# US 2014/0193632 A1 · Photosensitive alkali-soluble silicone resin composition

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- Number: US 2014/0193632 A1
- Document ID: US20140193632A1
- Status: Published application
- Kind: A1
- Application number: 14/241,700
- Filed: 2012-08-31
- Published: 2014-07-10
- Earliest claimed: 2011-08-31
- Assignees: Asahi Kasei E-Materials Corporation
- Inventors: Yamato Saito; Juri Iwama; Toru Katsumata; Yuka Sasaki; Masashi Kimura; Harumi Matsuda
- Web page: https://patentgrep.com/patent/US20140193632A1

## CPC

- C09D 183/06: containing silicon bound to oxygen-containing groups (C09D183/12 takes precedence)
- C08F 290/08: on to polymers modified by introduction of unsaturated side groups
- C08L 83/06: containing silicon bound to oxygen-containing groups (C08L83/12 takes precedence)
- C09D 163/04: Epoxynovolacs
- C09D 167/00: Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain (based on polyester-amides C09D177/12; based on polyester-imides C09D179/08); Coating compositions based on derivatives of such polymers
- C09D 175/04: Polyurethanes
- G03F 7/027: Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds (G03F7/075 takes precedence)
- 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 7/038: Macromolecular compounds which are rendered insoluble or differentially wettable (G03F7/075 takes precedence; macromolecular azides G03F7/012; macromolecular diazonium compounds G03F7/021)
- G03F 7/0388: {with ethylenic or acetylenic bands in the side chains of the photopolymer}
- G03F 7/0757: {Macromolecular compounds containing Si-O, Si-C or Si-N bonds (G03F7/0752 takes precedence)}
- C08F 230/085: {the monomer being a polymerisable silane, e.g. (meth)acryloyloxy trialkoxy silanes or vinyl trialkoxysilanes}
- C08G 77/14: containing silicon bound to oxygen-containing groups
- C08G 77/20: containing silicon bound to unsaturated aliphatic groups
- C09D: COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D)
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)
- 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)
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS

## Abstract

The present invention relates to a photosensitive alkali-soluble silicone resin composition comprising an alkali-soluble silicone resin (A) which comprises a carboxyl group or a dicarboxylic acid anhydride group in one molecule; an alkali-soluble resin (B) whose acid value is between 10 mgKOH/g and 200 mgKOH/g; and a photoinitiator (C). The (A) or (B) ingredient may comprise a photosensitive unsaturated double bond group, or the photosensitive alkali-soluble silicone resin composition may further comprise a compound (D) which comprises a photosensitive unsaturated double bond.

## Claims

### Claim 1

A photosensitive alkali-soluble silicone resin composition comprising:
(A) an alkali-soluble silicone resin having a carboxyl group or a dicarboxylic acid anhydride group in one molecule;
(B) an alkali-soluble resin (B) having an acid value of 10 to 200 mgKOH/g; and
(C) a photopolymerization initiator,
wherein said component (A) or (B) has a photopolymerizable unsaturated double bond group or said photosensitive alkali-soluble resin composition further contains (D) a photopolymerizable unsaturated double bond-containing compound.

### Claim 2 (depends on 1)

The photosensitive alkali-soluble silicone resin composition according to claim 1, wherein said alkali-soluble silicone resin (A) further contains a photopolymerizable unsaturated double bond group in one molecule.

### Claim 3 (depends on 1, 2)

The photosensitive alkali-soluble silicone resin composition according to claim 1 or 2, wherein said alkali-soluble silicone resin (A) is obtained by a reaction of:
(A-1) a silane compound represented by following formula (I):
R1R2aSi(R3)3-a (I)
{wherein R1 is a monovalent organic group containing a carboxyl group or a dicarboxylic acid anhydride group and having a carbon number of 4 to 20, R2 is a methyl group, R3 is at least one monovalent organic group selected from the group consisting of a methoxy group, an ethoxy group, a propoxy group and an isopropoxy group, a hydroxyl group or chloro group (Cl), and a is an integer of 0 or 1} and
(A-2) a silane compound represented by following formula (II):
R4bR5cSi(R3)4-b-c (II)
{wherein each of R4 and R5 is a group containing a photopolymerizable unsaturated double bond group or a polymerizable cyclic ether bond group and having a carbon number of 2 to 20, an aryl group having a carbon number of 6 to 20, an alkylaryl group having a carbon number of 2 to 20, an alkyl group having a carbon number of 1 to 20, which may be substituted with a mercapto group or an amino group, a cycloalkyl group having a carbon number of 5 to 20, or a group containing a carboxyl group or a dicarboxylic acid anhydride group and having a carbon number of 4 to 20, R4 and R5 may be the same or different and may be bonded to each other through a covalent bond, R3 is at least one monovalent organic group selected from the group consisting of a methoxy group, an ethoxy group, a propoxy group and an isopropoxy group, a hydroxyl group or Cl, b is an integer selected from 0 to 2, c is an integer of 0 or 1, but b+c does not exceed 2}.

### Claim 4 (depends on 1, 2)

The photosensitive alkali-soluble silicone resin composition according to claim 1 or 2, wherein said alkali-soluble silicone resin (A) is obtained by reacting:
said silane compound (A-1);
said silane compound (A-2); and
(A-3) a silanediol compound represented by following formula (III):
R62Si(OH)2 (III)
{wherein R6 is an aryl group having a carbon number of 6 to 20, an alkylaryl group having a carbon number of 2 to 20, an alkyl group having a carbon number of 1 to 20, which may be substituted with a mercapto group or an amino group, or a cycloalkyl group having a carbon number of 5 to 20, and a plurality of R6 may be the same or different and may be bonded to each other through a covalent bond},
in the presence of a catalyst.

### Claim 5 (depends on 1, 2)

The photosensitive alkali-soluble silicone resin composition according to claim 1 or 2, wherein said alkali-soluble silicone resin (A) further contains a polymerizable cyclic ether group in one molecule.

### Claim 6 (depends on 1, 2)

The photosensitive alkali-soluble silicone resin composition according to claim 1 or 2, wherein said alkali-soluble resin (B) contains a photopolymerizable unsaturated double bond group in one molecule.

### Claim 7 (depends on 1, 2)

The photosensitive alkali-soluble silicone resin composition according to claim 1 or 2, wherein said alkali-soluble resin (B) contains a photopolymerizable unsaturated double bond group and a carboxyl group or a dicarboxylic acid anhydride group in one molecule.

### Claim 8 (depends on 1, 2)

The photosensitive alkali-soluble silicone resin composition according to claim 1 or 2, wherein said alkali-soluble resin (B) is at least one polymer selected from the group consisting of a vinyl polymer composed of a reaction product of a polymerizable unsaturated double bond, an epoxy polymer composed of an addition reaction product of an epoxy group and a hydroxyl group, an aromatic methylene polymer composed of a reaction product of phenol and formaldehyde, a urethane polymer composed of a reaction product of dialcohol and diisocyanate, and an ester polymer composed of a reaction product of dicarboxylic acid and diepoxide.

### Claim 9 (depends on 1, 2)

The photosensitive alkali-soluble silicone resin composition according to claim 1 or 2, wherein the acid value (A)/acid value (B) ratio of the acid value (mgKOH/g) of said alkali-soluble silicone resin (A) to the acid value (mgKOH/g) of said alkali-soluble resin (B) is from 0.1 to 5.0.

### Claim 10 (depends on 1, 2)

The photosensitive alkali-soluble silicone resin composition according to claim 1 or 2, wherein both said alkali-soluble silicone resin (A) and said alkali-soluble resin (B) have a photopolymerizable unsaturated double bond group, and said photosensitive alkali-soluble silicone resin composition contains said photopolymerizable unsaturated double bond-containing compound (D).

### Claim 11 (depends on 1, 2)

The photosensitive alkali-soluble silicone resin composition according to claim 1 or 2, wherein with respect to the FT-IR spectrum of said photosensitive alkali-soluble silicone resin composition, the ratio (Iy/Ix) between the intensity (Ix) in the region of 1,000 to 1,100 cm−1 selected from the highest intensity when a maximum peak is not present, the intensity of one maximum peak when only one maximum peak is present, and the intensity of a highest maximum peak when a plurality of maximum peaks are present, and the intensity (Iy) in the region of 880 to 920 cm−1 selected from the highest intensity when a maximum peak is not present, the intensity of one maximum peak when only one maximum peak is present, and the intensity of a highest maximum peak when a plurality of maximum peaks are present, is from 0.01 to 0.4.

### Claim 12 (depends on 1, 2)

The photosensitive alkali-soluble silicone resin composition according to claim 1 or 2, wherein the three-dimensional crosslinking degree (T) as calculated from the integration ratio in the 29Si-NMR spectrum of said photosensitive alkali-soluble silicone resin composition according to following formula (IV) is 0.15 or less:
Three-dimensional crosslinking degree (T)=(AT3+AQ3+AQ4*2)/{(AM0+AM1)+(AD0+AD1+AD2)+(AT0+AT1+AT2+AT3)+(AQ0+AQ1+AQ2+AQ3+AQ4)} (formula IV).

### Claim 13 (depends on 1, 2)

The photosensitive alkali-soluble silicone resin composition according to claim 1 or 2, wherein the three-dimensional crosslinking degree (T′) as calculated from the integration ratio in the 29Si-NMR spectrum of said photosensitive alkali-soluble silicone resin composition according to following formula (V) is 0.3 or less:
Three-dimensional crosslinking degree (T′)=(AT3)/(AT0+AT1+AT2+AT3) (formula V).

### Claim 14

The photosensitive alkali-soluble silicone resin composition according toclaim 1 or 2, which contains:
from 1 to 98 mass % of said alkali-soluble silicone resin (A);
from 1 to 50 mass % of said alkali-soluble resin (B); and
from 0.01 to 15 mass % of said photopolymerization initiator (C),
based on the total solid content in said photosensitive alkali-soluble silicone resin composition.

### Claim 15 (depends on 1, 2)

The photosensitive alkali-soluble silicone resin composition according to claim 1 or 2, which contains:
from 1 to 98 mass % of said alkali-soluble silicone resin (A);
from 1 to 50 mass % of said alkali-soluble resin (B);
from 0.01 to 15 mass % of said photopolymerization initiator (C); and
from 5 to 45 mass % of said photopolymerizable unsaturated double bond-containing compound (D),
based on the total solid content in said photosensitive alkali-soluble silicone resin composition.

### Claim 16 (depends on 1, 2)

The photosensitive alkali-soluble silicone resin composition according to claim 1 or 2, which further contains (E) a solvent.

### Claim 17 (depends on 1, 2)

The photosensitive alkali-soluble silicone resin composition according to claim 1 or 2, which further contains (F) a hindered amine-based stabilizer.

### Claim 18 (depends on 17)

The photosensitive alkali-soluble silicone resin composition according to claim 17, wherein said hindered amine-based stabilizer (F) is contained in an amount of 0.001 to 15 mass % based on the mass of the total solid content in said photosensitive alkali-soluble silicone resin composition.

### Claim 19 (depends on 1, 2)

The photosensitive alkali-soluble silicone resin composition according to claim 1 or 2, wherein in a cured product obtained by curing said photosensitive alkali-soluble silicone resin composition, the transmittance of light at a wavelength of 400 nm under the conditions after baking said cured product having a thickness of 10 μm at 220° C. for 3 hours in an atmosphere is 70% or more.

### Claim 20 (depends on 1, 2)

A cured product obtained by curing the photosensitive alkali-soluble silicone resin composition according to claim 1 or 2.

### Claim 21 (depends on 1, 2)

A transparent insulating film obtained by curing the photosensitive alkali-soluble silicone resin composition according to claim 1 or 2.

### Claim 22

A cured product obtained by curing a resin composition comprising (G) a polyorganosiloxane, (H) an alkali-soluble resin except for said polyorganosiloxane (G), and (C) a photopolymerization initiator, wherein the three-dimensional crosslinking degree (T) as calculated from the integration ratio in the solid 29Si-NMR spectrum of said cured product according to following formula (IV) is 0.2 or less:
Three-dimensional crosslinking degree (T)=(AT3+AQ3+AQ4*2)/{(AM0+AM1)+(AD0+AD1+AD2)+(AT0+AT1+AT2+AT3)+(AQ0+AQ1+AQ2+AQ3+AQ4)} (formula IV).

### Claim 23

A cured product obtained by curing a resin composition comprising (G) a polyorganosiloxane, (H) an alkali-soluble resin except for said polyorganosiloxane (G), and (C) a photopolymerization initiator, wherein the three-dimensional crosslinking degree (T′) as calculated from the integration ratio in the solid 29Si-NMR spectrum of said cured product according to following formula (V) is 0.45 or less:
Three-dimensional crosslinking degree (T′)=(AT3)/(AT0+AT1+AT2+AT3) (formula V).

### Claim 24 (depends on 22, 23)

The cured product according to claim 22 or 23, wherein said polyorganosiloxane (G) is obtained by condensing a silane compound having a carboxylic acid group or a carboxylic acid anhydride group.

### Claim 25 (depends on 22, 23)

The cured product according to claim 22 or 23, wherein said polyorganosiloxane (G) contains a component in which the number of silicon (Si) atoms bonded to an oxygen (O) atom is two and/or a component in which the number of Si atoms bonded to an O atom is three.

### Claim 26 (depends on 22, 23)

The cured product according to claim 22 or 23, wherein said resin composition further contains at least one member selected from the group consisting of (F) a hindered amine-based stabilizer, (I) a photocrosslinkable monomer, (J) a silane coupling agent and (K) an ultraviolet absorber.

### Claim 27 (depends on 22, 23)

The cured product according to claim 22 or 23, wherein the glass transition temperature (Tg) of said cured product as measured by dynamic viscoelasticity measurement (DMA) is 80° C. or more.

### Claim 28 (depends on 22, 23)

The cured product according to claim 22 or 23, wherein said cured product has a thickness of 10 μm and the transmittance of light at a wavelength of 400 nm under the conditions after baking said cured product at 220° C. for 3 hours in an atmosphere is 70% or more.