# US 8,771,924 B2 · Polymerizable composition, lithographic printing plate precursor and lithographic printing method

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- Number: US 8,771,924 B2
- Document ID: US8771924B2
- Status: Granted
- Kind: B2
- Application number: 11/964,125
- Filed: 2007-12-26
- Published: 2008-08-21
- Granted: 2014-07-08
- Earliest claimed: 2006-12-26
- Assignees: FUJIFILM Corporation
- Applicants: Hidekazu Oohashi
- Inventors: Hidekazu Oohashi
- Web page: https://patentgrep.com/patent/US8771924B2

## CPC

- B41N 1/08: for lithographic printing {(B41N1/003, B41N3/03 take precedence; compositions of the image-forming layer B41C1/10)}
- B41C 1/1008: {by removal or destruction of lithographic material on the lithographic support, e.g. by laser or spark ablation; by the use of materials rendered soluble or insoluble by heat exposure, e.g. by heat produced from a light to heat transforming system; by on-the-press exposure or on-the-press development, e.g. by the fountain of photolithographic materials}
- G03F 7/032: with binders
- G03F 7/033: the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
- G03F 7/035: the binders being polyurethanes
- G03F 7/037: the binders being polyamides or polyimides
- G03F 7/2055: {for the production of printing plates; Exposure of liquid photohardening compositions}
- G03F 7/3035: {from printing plates fixed on a cylinder or on a curved surface; from printing cylinders}
- B41C 1/1016: {characterised by structural details, e.g. protective layers, backcoat layers or several imaging layers}
- B41C 2201/02: Cover layers; Protective layers
- B41C 2201/06: Backcoats; Back layers
- B41C 2201/10: characterised by inorganic compounds, e.g. pigments
- B41C 2201/12: characterised by non-macromolecular organic compounds
- B41C 2201/14: characterised by macromolecular organic compounds, e.g. binder, adhesives
- B41C 2210/04: Negative working, i.e. the non-exposed (non-imaged) areas are removed
- B41C 2210/06: Developable by an alkaline solution
- B41C 2210/08: Developable by water or the fountain solution
- B41C 2210/20: characterised by inorganic additives, e.g. pigments, salts
- B41C 2210/22: characterised by organic non-macromolecular additives, e.g. dyes, UV-absorbers, plasticisers
- B41C 2210/24: characterised by a macromolecular compound or binder obtained by reactions involving carbon-to-carbon unsaturated bonds, e.g. acrylics, vinyl polymers
- B41N: PRINTING PLATES OR FOILS (photosensitive material G03); MATERIALS FOR SURFACES USED IN PRINTING MACHINES FOR PRINTING, INKING, DAMPING, OR THE LIKE; PREPARING SUCH SURFACES FOR USE AND CONSERVING THEM
- B41C: PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES (photomechanical processes for producing printing surfaces G03F; photoelectrical processes for producing printing surfaces G03G)
- G03F: PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR; (phototypographic composing devices B41B; photosensitive materials or processes for photographic purposes G03C; electrophotography, sensitive layers or processes therefor G03G)

## Abstract

A polymerizable composition contains a binder polymer containing a functional group having a dipole moment of 3.8 debye or more and being represented by the formula (1), (2), (3), (4) or (5) as defined herein, a radical polymerizable compound and a radical polymerization initiator.

## Claims

### Claim 1

A polymerizable composition comprising a binder polymer containing a functional group having a dipole moment of 4.5 debye or more, a radical polymerizable compound which is an addition polymerizable compound having at least one ethylenically unsaturated double bond, an infrared absorbing agent or a sensitizing dye having absorption in a wavelength of from 360 to 450 nm and a radical polymerization initiator,
wherein the functional group having a dipole moment of 4.5 debye or more is selected from the following groups:

### Claim 2

A polymerizable composition comprising a binder polymer containing a functional group having a dipole moment of 3.8 debye or more and being represented by the following formula (1), (2), (3) (4) or (5), a radical polymerizable compound which is an addition polymerizable compound having at least one ethylenically unsaturated double bond and a radical polymerization initiator:
wherein X and Y each independently represents —C(R5)(R6)—, —C(R5)═, —O—, —S—, —N(R)5— or —N═, Z1 represents O or S, Z2 represents 0 or a lone pair, Z3 represents —C(R5)(R6)—, C(R5)═, —O—, —S—, —N(R5)— or —N═, R1 to R6 each independently represents a substituent comprising at least one atom selected from hydrogen, carbon, oxygen, nitrogen, sulfur, phosphorus, halogen and silicon or appropriate two of R1 to R6 may be combined with each other to form a ring, provided that at least one of R1 to R6 represents a divalent connecting group comprising at least one atom selected from hydrogen, carbon, oxygen, nitrogen, sulfur, phosphorus, halogen and silicon and connecting to a skeleton of the binder polymer,
wherein the functional group having a dipole moment of 3.8 debye or more and being represented by the formula (1), (2), (3), (4) or (5) is selected from the following groups:
Groups of Formula (2):
3.9
4.0
5.4
4.3
5.5
5.6
4.1
5.4
4.8
5.4
5.1
5.1
4.7
5.5
5.3
4.9
6.3
4.1
6.2
5.3
3.9
5.8
4.6
4.7
4.9
4.4
4.9
4.7
4.1
3.9
4.1
3.9
4.7
4.7
Grops of Formulae (3) to (5):
5.0
5.3
4.1
4.9
5.9
4.6
5.2
4.1
5.3
5.1
4.7
4.7
6.9
5.2
wherein the binder polymer has a repeating unit selected from the following formulae:
Units U-4, U-8, U-25, U-30, U-32, U-36, U-42, U-55, U-56, U-59 to U-104, U-106 to U-109, U-115, U-118, U-121, U-123, U-127 to U-130, U-132 to U-134, V-2 to V-11, V-13 to V-17, V-20 to V-22, V-24 to V-26, V-30, V-33 to V-36, V-38, V-40 and V-43 to V-45:

### Claim 3 (depends on 2)

The polymerizable composition as claimed in claim 2, wherein the binder polymer has a repeating unit selected from the following formulae:
Units U-4, U-8, U-25, U-30, U-32, U-36, U-42, U-55, U-56, U-63, U-69, U-83, U-84, U-95, U-115, U-118, U-121, U-130, V-2, V-3, V-4, V-6, V-7, V-8, V-9, V-11, V-13 to V-17, V-28, V-33 to V-36, V-40 and V-43 to V-45.

### Claim 4 (depends on 2)

The polymerizable composition as claimed in claim 2, wherein the binder polymer includes more than 20% by mole of the repeating unit.

### Claim 5

A polymerizable composition comprising a binder polymer containing a functional group having a dipole moment of 3.8 debye or more and being represented by the following formula (1), (2), (3) (4) or (5), a radical polymerizable compound which is an addition polymerizable compound having at least one ethylenically unsaturated double bond and a radical polymerization initiator:
wherein X and Y each independently represents —C(R5)(R6)—, —C(R5)═, —O—, —S—, —N(R)5— or —N═, Z1 represents O or S, Z2 represents O or a lone pair, Z3 represents —C(R5)(R6)—, C(R5)═, —O—, —S—, —N(R5)— or —N═, R1 to R6 each independently represents a substituent comprising at least one atom selected from hydrogen, carbon, oxygen, nitrogen, sulfur, phosphorus, halogen and silicon or appropriate two of R1 to R6 may be combined with each other to form a ring, provided that at least one of R1 to R6 represents a divalent connecting group comprising at least one atom selected from hydrogen, carbon, oxygen, nitrogen, sulfur, phosphorus, halogen and silicon and connecting to a skeleton of the binder polymer,
wherein the functional group having a dipole moment of 3.8 debye or more and being represented by the following formula (1), (2), (3), (4) or (5) is selected from the following groups:
Groups of Formula (2):
3.9
4.0
5.4
4.3
5.5
5.6
4.1
5.4
4.8
5.4
5.1
5.1
4.7
5.5
5.3
4.9
6.3
4.1
6.2
5.3
3.9
5.8
4.6
4.7
4.9
4.4
4.9
4.7
4.1
3.9
4.1
3.9
4.7
4.7
Grops of Formulae (3) to (5):
5.0
5.3
4.1
4.9
5.9
4.6
5.2
4.1
5.3
5.1
4.7
4.7
6.9
5.2
wherein the binder polymer is represented by one of the following structural formulae:
Binder polymers B-4, B-8, B-16, B-17, B-25, B-30 to B-32, B-36, B-42, B-55, B-56, B-59 to B-104, B-106, B-109, B-115, B-118, B-121 and B-123, B-127 to B-130, B-132 to B-134, B-136 to B-187 and B-190 to B-199, where the percentages of the constituent units are mole percentages:
Unit 1
Unit 2
Unit 3
Binder
Content
Content
Content
Polymer
No.
(%)
No.
(%)
No.
(%)
B-1
U-1
20
N-12
20
N-1
60
B-2
U-2
30
N-19
10
N-15
60
B-3
U-3
40
N-14
20
N-16
40
B-4
U-4
50
N-1
12
N-12
38
B-5
U-5
20
N-21
10
N-10
70
B-6
U-6
20
N-11
20
N-18
60
B-7
U-7
30
N-33
20
N-6
50
B-8
U-8
60
N-7
25
N-19
15
B-9
U-9
30
N-34
20
N-7
50
B-10
U-10
20
N-28
10
N-22
70
B-11
U-11
30
N-35
20
N-27
50
B-12
U-12
30
N-42
12
N-44
58
B-13
U-13
90
N-43
10
—
—
B-14
U-14
80
N-50
20
—
—
B-15
U-15
80
N-57
20
—
—
B-16
U-16
40
N-48
10
N-52
50
B-17
U-17
30
N-49
20
N-1
50
B-18
U-18
50
N-63
12
N-15
38
B-19
U-19
90
N-51
10
—
—
B-20
U-20
80
N-58
20
—
—
B-21
U-21
80
N-33
20
—
—
B-22
U-22
40
N-56
10
N-16
50
B-23
U-23
20
N-12
20
N-10
60
B-24
U-24
30
N-19
12
N-18
58
B-25
U-25
85
N-12
15
—
—
B-26
U-26
80
N-14
20
—
—
B-27
U-27
60
N-21
10
N-6
30
B-28
U-28
60
N-11
20
N-7
20
B-29
U-29
30
N-33
12
N-22
58
B-30
U-30
70
N-12
10
N-7
20
B-31
U-31
80
N-12
20
—
—
B-32
U-32
90
N-33
10
—
—
B-33
U-33
50
N-34
20
N-27
30
B-34
U-34
40
N-28
10
N-44
50
B-35
U-35
70
N-35
20
N-6
10
B-36
U-36
90
N-12
10
—
—
B-37
U-37
80
N-42
20
—
—
B-38
U-38
50
N-43
10
N-1
40
B-39
U-39
30
N-50
20
N-15
50
B-40
U-40
60
N-12
30
N-10
10
B-41
U-41
90
N-57
10
—
—
B-42
U-42
60
N-33
10
N-6
30
B-43
U-43
80
N-48
20
—
—
B-44
U-44
40
N-49
10
N-16
50
B-45
U-45
30
N-63
20
N-10
50
Unit 1
Unit 2
Unit 3
Binder
Content
Content
Content
Polymer
No.
(%)
No.
(%)
No.
(%)
B-46
U-46
30
N-51
12
N-18
58
B-47
U-47
90
N-58
10
—
—
B-48
U-48
80
N-56
20
—
—
B-49
U-49
80
N-12
20
—
—
B-50
U-50
90
N-19
10
—
—
B-51
U-51
30
N-14
20
N-6
50
B-52
U-52
40
N-21
12
N-7
48
B-53
U-53
40
N-11
10
N-22
50
B-54
U-54
80
N-33
20
—
—
B-55
U-55
70
N-35
10
N-6
20
B-56
U-56
30
N-34
12
N-27
58
B-57
U-57
60
N-28
10
N-44
30
B-58
U-58
50
N-35
20
N-52
30
B-59
U-59
60
N-42
10
N-6
30
B-60
U-60
80
N-42
20
—
—
B-61
U-61
90
N-43
10
—
—
B-62
U-62
80
N-50
20
—
—
B-63
U-63
88
N-14
12
—
—
B-64
U-64
88
N-57
12
—
—
B-65
U-65
50
N-48
10
N-1
40
B-66
U-66
30
N-49
20
N-15
50
B-67
U-67
50
N-63
10
N-16
40
B-68
U-68
80
N-51
20
—
—
B-69
U-69
70
N-43
10
N-28
20
B-70
U-70
80
N-58
20
—
—
B-71
U-71
30
N-56
10
N-10
60
B-72
U-72
60
N-12
20
N-18
20
B-73
U-73
50
N-19
12
N-6
38
B-74
U-74
30
N-14
10
N-7
60
B-75
U-75
30
N-21
20
N-22
50
B-76
U-76
30
N-11
20
N-27
50
B-77
U-77
90
N-33
10
—
—
B-78
U-78
60
N-34
20
N-44
20
B-79
U-79
50
N-28
12
N-52
38
B-80
U-80
60
N-35
10
N-1
30
B-81
U-81
80
N-42
20
—
—
B-82
U-82
80
N-43
20
—
—
B-83
U-83
90
N-50
10
—
—
B-84
U-84
70
N-33
30
—
—
B-85
U-85
30
N-57
12
N-15
58
B-86
U-86
30
N-48
10
N-16
60
B-87
U-87
80
N-49
20
—
—
B-88
U-88
80
N-63
20
—
—
Unit 1
Unit 2
Unit 3
Binder
Content
Content
Content
Polymer
No.
(%)
No.
(%)
No.
(%)
B-89
U-89
90
N-51
10
—
—
B-90
U-90
80
N-58
20
—
—
B-91
U-91
50
N-56
12
N-10
38
B-92
U-92
40
N-12
10
N-18
50
B-93
U-93
50
N-19
20
N-6
30
B-94
U-94
80
N-14
20
—
—
B-95
U-95
80
N-12
20
—
—
B-96
U-96
30
N-21
20
N-7
50
B-97
U-97
30
N-11
10
N-22
60
B-98
U-98
40
N-33
20
N-27
40
B-99
U-99
88
N-34
12
—
—
B-100
U-100
90
N-28
10
—
—
B-101
U-101
80
N-35
20
—
—
B-102
U-102
60
N-42
20
N-44
20
B-103
U-103
50
N-49
10
N-18
40
B-104
U-104
60
N-12
30
N-1
10
B-105
U-105
88
N-50
12
—
—
B-106
U-106
90
N-57
10
—
—
B-107
U-107
30
N-48
20
N-1
50
B-108
U-108
30
N-49
20
N-15
50
B-109
U-109
40
N-63
10
N-16
50
B-110
U-110
80
N-51
20
—
—
B-111
U-111
88
N-58
12
—
—
B-112
U-112
90
N-56
10
—
—
B-113
U-113
50
N-12
20
N-10
30
B-114
U-114
50
N-19
20
N-18
30
B-115
U-115
50
N-14
10
N-6
40
B-116
U-116
50
N-21
20
N-7
30
B-117
U-117
40
N-11
12
N-22
48
B-118
U-118
50
N-33
10
N-27
40
B-119
U-119
80
N-34
20
—
—
B-120
U-120
80
N-28
20
—
—
B-121
U-121
60
N-56
30
N-44
10
B-122
U-122
80
N-35
20
—
—
B-123
U-123
90
N-42
10
—
—
B-124
U-124
80
N-43
20
—
—
B-125
U-125
70
N-51
30
—
—
B-126
U-126
60
N-50
10
N-44
30
B-127
U-127
60
N-57
20
N-52
20
B-128
U-128
40
N-48
12
N-1
48
B-129
U-129
80
N-49
20
—
—
B-130
U-130
80
N-51
20
—
—
B-131
U-131
50
N-63
20
N-15
30
Binder
Unit 1
Unit 2
Unit 3
Polymer
No.
Content (%)
No.
No.
Content (%)
B-132
U-132
50
N-51
10
N-16
40
B-133
U-133
30
N-58
20
N-10
50
B-134
U-134
80
N-56
20
—
—
B-135
U-135
70
N-51
20
N-52
10
B-136
U-136
50
N-12
20
N-18
30
B-137
U-137
50
N-19
20
N-6
30
B-138.
U-138
50
N-14
20
N-7
30
B-139
U-139
50
N-21
20
N-22
30
B-140
U-140
50
N-11
20
N-27
30
B-141
U-141
50
N-33
20
N-44
30
B-142
U-142
50
N-34
20
N-52
30
B-143
U-143
50
N-28
20
N-1
30
B-144
U-144
50
N-58
20
N-44
30
B-145
U-145
50
N-35
20
N-15
30
B-146
U-146
50
N-42
20
N-16
30
B-147
U-147
50
N-43
20
N-10
30
B-148
U-148
50
N-50
20
N-18
30
B-149
U-149
60
N-51
20
N-52
20
B-150
U-150
70
N-51
20
N-44
10
Unit 1
Unit 2
Unit 3
Unit 4
Unit 5
Binder
Content
Content
Content
Content
Content
Polymer
No.
(%)
No.
(%)
No.
(%)
No.
(%)
No.
(%)
B-151
V-47
30
N-74
20
V-1
20
N-64
20
N-71
10
B-152
V-47
50
V-2
30
N-65
10
N-64
10
—
—
B-153
V-48
40
N-79
10
V-3
30
N-85
10
N-72
10
B-154
N-66
30
N-68
20
V-4
25
N-71
20
N-88
5
B-155
V-49
30
N-68
20
V-5
42
N-86
8
—
—
B-156
V-51
40
N-96
10
V-6
25
N-87
15
N-64
10
B-157
N-67
20
N-97
30
V-7
40
N-88
10
—
—
B-158
N-68
20
N-74
30
V-8
30
N-90
10
N-72
10
B-159
N-95
30
V-50
20
V-9
20
N-64
20
N-78
10
B-160
V-47
40
N-81
10
V-10
30
N-65
10
N-78
10
B-161
N-73
20
N-98
30
V-11
35
N-71
10
N-86
5
B-162
N-74
30
N-81
20
V-12
35
N-85
15
—
—
B-163
N-79
30
N-96
20
V-13
42
N-86
8
—
—
B-164
N-80
25
N-68
25
V-14
35
N-87
15
—
—
B-165
N-81
20
N-79
30
V-15
40
N-88
10
—
—
B-166
V-49
50
V-16
25
N-85
15
N-72
10
—
—
B-167
N-96
30
N-80
20
V-17
25
N-90
20
N-78
5
B-168
N-98
25
N-79
25
V-18
30
N-64
10
N-87
10
B-169
N-97
50
V-19
40
N-65
10
—
—
—
—
B-170
V-48
50
V-20
35
N-86
5
N-71
10
—
—
B-171
N-66
10
N-68
40
V-21
30
N-87
10
N-64
10
B-172
N-67
30
N-96
20
V-22
30
N-71
10
N-65
10
B-173
N-68
50
V-23
30
N-85
10
N-78
10
—
—
B-174
V-51
50
V-24
40
N-88
10
—
—
—
—
B-175
N-95
30
N-81
20
V-25
32
N-86
8
N-78
10
B-176
N-73
30
N-97
20
V-26
35
N-87
15
—
—
B-177
N-74
30
N-96
20
V-27
40
N-88
10
—
—
B-178
N-79
25
N-98
25
V-24
20
N-90
20
N-72
10
B-179
N-74
30
N-81
20
V-16
20
N-90
10
N-72
20
B-180
V-47
50
N-86
10
N-72
20
N-78
20
—
—
B-181
V-49
20
V-47
30
N-88
10
N-72
20
N-78
20
Unit 1
Unit 2
Unit 3
Unit 4
Unit 5
Binder
Content
Content
Content
Content
Content
Polymer
No.
(%)
No.
(%)
No.
(%)
No.
(%)
No.
(%)
B-182
V-51
25
V-48
25
V-2
30
N-90
10
N-72
10
B-183
V-47
50
N-75
15
V-29
30
N-69
5
—
—
B-184
V-48
40
N-96
10
N-82
20
V-30
30
—
—
B-185
N-74
20
N-97
30
N-75
15
V-31
35
—
—
B-186
N-95
20
N-68
30
N-82
20
V-32
20
N-69
10
B-187
N-73
10
N-79
40
N-75
15
V-33
25
N-69
10
B-188
V-49
50
N-82
20
V-34
30
—
—
—
—
B-189
N-67
20
N-81
30
N-75
10
V-35
20
N-69
20
B-190
V-51
50
N-82
30
V-36
20
—
—
—
—
B-191
N-98
50
N-75
15
V-37
20
N-69
15
—
—
B-192
N-79
30
N-98
20
N-82
20
V-38
20
N-69
10
B-193
N-74
30
N-81
20
N-82
20
V-34
15
V-36
15
B-194
V-51
25
V-48
25
N-75
20
N-69
30
—
—
B-195
V-39
30
N-76
20
N-85
10
N-72
20
N-78
20
B-196
V-40
50
V-2
20
N-90
10
V-16
20
—
—
B-197
V-41
30
V-44
20
V-16
25
N-85
15
N-72
10
B-198
V-42
30
N-83
20
V-24
40
N-88
10
—
—
B-199
V-43
30
N-76
20
N-75
20
N-69
30
—
—
B-200
V-44
30
V-39
20
N-82
20
V-34
15
V-36
15
B-201
V-45
20
N-83
30
N-82
20
V-30
30
—
—
B-202
V-46
20
N-83
30
N-75
20
N-69
30
—
—
B-203
N-83
20
N-76
30
V-2
20
N-90
10
V-16
20
B-204
N-83
30
N-76
20
N-82
20
V-34
15
V-36
15
B-205
V-52
20
N-70
30
N-88
10
N-72
20
N-78
20
B-206
V-53
40
N-77
10
N-85
10
V-2
40
—
—
B-207
N-70
20
N-77
30
N-85
10
V-2
40
—
—
B-208
V-52
25
V-53
25
V-2
25
V-16
25
—
—
wherein the structures of the U, V and N units of the binder polymer are as follows:

### Claim 6 (depends on 5)

The polymerizable composition as claimed in claim 5, wherein the binder polymer is represented by one of the following structural formulae:
Binder polymers B-4, B-8, B-25, B-30 to B-32, B-36, B-42, B-55, B-56, B-63, B-69, B-83, B-84, B-95, B-115, B-118, B-121, B-130, B-137 to B-139, B-142 to B-144, B-146 and B-148 to B-152.

### Claim 7 (depends on 1)

The polymerizable composition as claimed in claim 1, wherein the binder polymer has an acid value of 0.3 meq/g or less.

### Claim 8 (depends on 1)

An image-forming material comprising a support and a layer comprising the polymerizable composition as claimed in claim 1.

### Claim 9 (depends on 1)

A lithographic printing plate precursor comprising a support of a hydrophilic surface and a photosensitive layer comprising the polymerizable composition as claimed in claim 1.

### Claim 10 (depends on 9)

The lithographic printing plate precursor as claimed in claim 9, which comprises a protective layer, so that the support, the photosensitive layer and the protective layer are provided in this order.

### Claim 11 (depends on 1)

The lithographic printing plate precursor as claimed in claim 1, which is capable of performing printing by mounting on a printing machine after image exposure without carrying out a development processing step.

### Claim 12 (depends on 11)

A lithographic printing method comprising:
(i) mounting the lithographic printing plate precursor as claimed in claim 11 on a printing machine and exposing the mounted lithographic printing plate precursor imagewise with a laser or (ii) exposing the lithographic printing plate precursor as claim 11 imagewise with a laser and mounting the exposed lithographic printing plate precursor on a printing machine; and
supplying printing ink and dampening water on the exposed lithographic printing plate precursor to remove an unexposed area of the photosensitive layer and printing.

### Claim 13 (depends on 1)

The polymerizable composition as claimed in claim 1, wherein the functional group has a dipole moment of 5.0 debye or more and the functional group having a dipole moment of 5.0 debye or more is selected from the following groups:

### Claim 14 (depends on 1)

The polymerizable composition as claimed in claim 1, wherein the binder polymer is a resin selected from the group consisting of an acrylic resin, a methacrylic resin, a styrene resin, a urethane resin, a urea resin, an amide resin, an ester resin and a carbonate resin.

### Claim 15 (depends on 1)

The polymerizable composition as claimed in claim 1, wherein the binder polymer is a resin selected from the group consisting of an acrylic resin, a methacrylic resin and a urethane resin.