# US 2019/0375896 A1 · Silsesquioxane derivative having radical polymerizable functional group, composition thereof, and cured film having low cure shrinkage

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- Number: US 2019/0375896 A1
- Document ID: US20190375896A1
- Status: Published application
- Kind: A1
- Application number: 16/476,798
- Filed: 2018-01-09
- Published: 2019-12-12
- Earliest claimed: 2017-01-10
- Assignees: Jnc Corporation; Jnc Petrochemical Corporation
- Applicants: Jnc Corporation; Jnc Petrochemical Corporation
- Inventors: Kazuya SUWA; Hironori IKENO; Tomoyuki OOBA
- Web page: https://patentgrep.com/patent/US20190375896A1

## CPC

- C09D 183/04: Polysiloxanes
- C07F 7/10: containing nitrogen {having a Si-N linkage}
- C08F 2/50: with sensitising agents
- C08F 222/1006: {of polyhydric alcohols or polyhydric phenols}
- C08F 230/085: {the monomer being a polymerisable silane, e.g. (meth)acryloyloxy trialkoxy silanes or vinyl trialkoxysilanes}
- C08G 77/045: {containing less than 25 silicon atoms}
- C08G 77/20: containing silicon bound to unsaturated aliphatic groups
- C08G 77/26: nitrogen-containing groups
- C08G 77/38: Polysiloxanes modified by chemical after-treatment
- C09D 4/06: {Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond} in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
- C09D 135/02: Homopolymers or copolymers of esters (C09D135/06, C09D135/08 take precedence)
- C09D 143/04: Homopolymers or copolymers of monomers containing silicon
- C09D 183/06: containing silicon bound to oxygen-containing groups (C09D183/12 takes precedence)
- C09D 183/08: containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
- C09D 183/12: containing polyether sequences
- C09J 135/00: Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least another carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Adhesives based on derivatives of such polymers
- H05K 1/0346: {containing N}
- C08G 77/14: containing silicon bound to oxygen-containing groups
- C08G 77/46: containing polyether sequences
- H05K 3/287: {Photosensitive compositions}
- 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)
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C09J: ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES (preparation of glue or gelatine C09H)
- H05K: PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS

## Abstract

Provided is a new compound which can provide a cured film obtained from a resin composition with low cure shrinkage while suppressing reduction of hardness (scratch resistance) thereof. A silsesquioxane derivative having a radically polymerizable functional group, which is represented by formula (1), (2) or (3). In the formulas (1) to (3), R1 is a group independently selected from alkyl having 1 to 45 carbons, cycloalkyl having 4 to 8 carbons, aryl having 6 to 14 carbons and arylalkyl having 7 to 24 carbons, R2 and R3 are a group independently selected from alkyl having 1 to 10 carbons, cyclopentyl, cyclohexyl and phenyl, and X is independently hydrogen or a monovalent organic group, in which at least one of X is a radically polymerizable functional group represented by formula (4).

## Claims

### Claim 1

A silsesquioxane derivative having a radically polymerizable functional group, represented by formula (1), (2) or (3):
wherein, in the formulas (1) to (3),
R1 is a group independently selected from alkyl having 1 to 45 carbons, cycloalkyl having 4 to 8 carbons, aryl having 6 to 14 carbons and arylalkyl having 7 to 24 carbons; in the alkyl having 1 to 45 carbons, at least one hydrogen may be replaced by fluorine, and at least one non-adjacent —CH2— may be replaced by —O— or —CH═CH—; in a benzene ring in the aryl and the arylalkyl, at least one hydrogen may be replaced by halogen or alkyl having 1 to 10 carbons, and in the alkyl having 1 to 10 carbons, at least one hydrogen may be replaced by fluorine, and at least one non-adjacent —CH2— may be replaced by —O— or —CH═CH—; the number of carbons of alkylene in the arylalkyl is 1 to 10, and at least one non-adjacent —CH2— may be replaced by —O—;
R2 and R3 are a group independently selected from alkyl having 1 to 10 carbons, cyclopentyl, cyclohexyl and phenyl,
X is independently hydrogen or a monovalent organic group, in which at least one of X is a radically polymerizable functional group represented by formula (4); and
in formula (4), 1 is an integer from 0 to 10, m is an integer from 0 to 10, n is 0 or 1, p is an integer from 0 to 10, q is 0 or 1, r is 0 or 1, s is an integer from 0 to 10, R4 is a hydroxyl group, R5 is hydrogen or methyl, R6 is an organic group having 4 to 6 carbons, and having an acryloyl group or a methacryloyl group, and R7 is hydrogen or methyl; and arbitrary —CH2— may be replaced by —O—; in which a case where two oxygens are bonded with each other (—O—O—) is excluded; in X of the silsesquioxane derivative represented by formula (1), when all of m, n, p, q and r are 0, and R7 is methyl, a sum: 1+s is an integer from 4 or more; and in X of the silsesquioxane derivative represented by formula (2), when all of m, n, p, q and r are 0, a sum: 1+s is an integer from 4 or more:

### Claim 2 (depends on 1)

The silsesquioxane derivative having the radically polymerizable functional group according to claim 1, wherein, in the formula (1), (2) or (3), all of R2 and R3 are alkyl having 1 to 6 carbons.

### Claim 3 (depends on 2)

The silsesquioxane derivative having the radically polymerizable functional group according to claim 2, wherein, in the formula (1), (2) or (3), all of R2 and R3 are a methyl group or an ethyl group.

### Claim 4 (depends on 1)

The silsesquioxane derivative having the radically polymerizable functional group according to claim 1, wherein, in the formula (1), (2) or (3), all of X contain a polymerizable functional group.

### Claim 5 (depends on 1)

The silsesquioxane derivative having the radically polymerizable functional group according to claim 1, wherein, in the formula (1), (2) or (3), at least one of X is (meth)acrylate, urethane (meth)acrylate or epoxy (meth)acrylate.

### Claim 6 (depends on 1)

The silsesquioxane derivative having the radically polymerizable functional group according to claim 1, wherein, in the formula (1), X is one kind selected from the group of polymerizable functional groups represented by (a-1) to (a-4), (b-1) to (b-5), (c-1), (c-2), (d-1) and (d-2),
in the formula (2), X is one kind selected from the group of polymerizable functional groups represented by (a-1) to (a-3), (b-1) to (b-5), (c-1), (c-2), (d-1) and (d-2), and
in the formula (3), X is one kind selected from the group of polymerizable functional groups represented by (a-1) to (a-5), (b-1) to (b-5), (c-1), (c-2), (d-1) and (d-2):
wherein, R4 is a hydroxyl group, and p is an integer from 0 to 10.

### Claim 7

A resin composition, containing acrylic resin (A) and at least one kind selected from silsesquioxane derivatives (B) represented by formula (1), (2) or (3),
wherein, in the silsesquioxane derivative represented by formula (1), (2) or (3),
R1 is a group independently selected from alkyl having 1 to 45 carbons, cycloalkyl having 4 to 8 carbons, aryl having 6 to 14 carbons and arylalkyl having 7 to 24 carbons; and in the alkyl having 1 to 45 carbons, at least one hydrogen may be replaced by fluorine, and at least one non-adjacent-CH2— may be replaced by —O— or —CH═CH—; in a benzene ring in the aryl and the arylalkyl, at least one hydrogen may be replaced by halogen or alkyl having 1 to 10 carbons, and in the alkyl having 1 to 10 carbons, at least one hydrogen may be replaced by fluorine, and at least one non-adjacent —CH2— may be replaced by —O— or —CH═CH—; the number of carbons of alkylene in the arylalkyl is 1 to 10, and at least one non-adjacent-CH2— may be replaced by —O—,
R2 and R3 are a group independently selected from alkyl having 1 to 10 carbons, cyclopentyl, cyclohexyl and phenyl,
X is independently hydrogen or a monovalent organic group, in which at least one of X is a radically polymerizable functional group represented by formula (4); and
in formula (4), 1 is an integer from 0 to 10, m is an integer from 0 to 10, n is 0 or 1, p is an integer from 0 to 10, q is 0 or 1, r is 0 or 1, s is an integer from 0 to 10, R4 is a hydroxyl group, R5 is hydrogen or methyl, R6 is an organic group having 4 to 6 carbons, and having an acryloyl group or a methacryloyl group, R7 is hydrogen or methyl; and arbitrary —CH2— may be replaced by —O—; in which a case where two oxygens are bonded with each other (—O—O—) is excluded, in X of the silsesquioxane derivative represented by formula (1), when all of m, n, p, q and r are 0, and R7 is methyl, a sum: 1+s is an integer from 4 or more, and in X of the silsesquioxane derivative represented by formula (2), when all of m, n, p, q and r are 0, a sum: 1+s is an integer from 4 or more:

### Claim 8 (depends on 7)

The resin composition according to claim 7, containing at least one kind of a silsesquioxane derivative, wherein, in the silsesquioxane derivative (B) represented by formula (1), (2) or (3), all of R1 are phenyl, all of R2 and R3 are a methyl group, and X is selected from the group represented by (a-1) to (a-5), (b-1) to (b-5), (c-1), (c-2), (d-1) and (d-2):
wherein, R4 is a hydroxyl group and p is an integer from 0 to 10.

### Claim 9 (depends on 7)

The resin composition according to claim 7, wherein the acrylic resin (A) is a polyfunctional monomer type (meth)acrylic resin.

### Claim 10 (depends on 7)

The resin composition according to claim 7, containing acrylic resin(A) by 10% by mass or more and 95% by mass or less in a solid content of the resin composition.

### Claim 11 (depends on 7)

The resin composition according to claim 7, wherein a mass ratio of a content of the acrylic resin (A) to a total content of the silsesquioxane derivatives (B) represented by formula (1), (2) or (3) is 10:90 to 95:5.

### Claim 12 (depends on 7)

A cured film, formed by curing the resin composition according to claim 7.

### Claim 13

A laminate, including:
a base material; and
a cured film formed by curing the resin composition containing at least acrylic resin (A) and at least one kind selected from silsesquioxane derivatives (B) represented by formula (1), (2) or (3) on the base material, and the laminate,
in which a warpage height of the base material with the cured film, on the resin composition, is 0 millimeter or more and 4 millimeters or less by evaluation method 1, and adhesion after 120 hours is rated to be 4B or more for all in an adhesion evaluation by evaluation method 2: and in the formulas (1) to (3), R1 is a group independently selected from alkyl having 1 to 45 carbons, cycloalkyl having 4 to 8 carbons, aryl having 6 to 14 carbons and arylalkyl having 7 to 24 carbons; and in the alkyl having 1 to 45 carbons, at least one hydrogen may be replaced by fluorine, and at least one non-adjacent —CH2— may be replaced by —O— or —CH═CH—; in a benzene ring in the aryl and the arylalkyl, at least one hydrogen may be replaced by halogen or alkyl having 1 to 10 carbons, and in the alkyl having 1 to 10 carbons, at least one hydrogen may be replaced by fluorine, and at least one non-adjacent —CH2— may be replaced by —O— or —CH═CH—; and the number of carbons of alkylene in the arylalkyl is 1 to 10, and at least one non-adjacent-CH2— may be replaced by —O—,
R2 and R3 are a group independently selected from alkyl having 1 to 10 carbons, cyclopentyl, cyclohexyl and phenyl,
X is independently hydrogen or a monovalent organic group, in which at least one of X is a radically polymerizable functional group represented by formula (4); and
in the formula (4), 1 is an integer from 0 to 10, m is an integer from 0 to 10, n is 0 or 1, p is an integer from 0 to 10, q is 0 or 1, r is 0 or 1, s is an integer from 0 to 10, R4 is a hydroxyl group, R5 is hydrogen or methyl, R6 is an organic group having 4 to 6 carbons, and having an acryloyl group or a methacryloyl group, and R7 is hydrogen or methyl; and arbitrary —CH2— may be replaced by —O—; in which a case where two oxygens are bonded with each other (—O—O—) is excluded; in X of the silsesquioxane derivative represented by formula (1), when all of m, n, p, q and r are 0 and R7 is methyl, a sum: 1+s is an integer from 4 or more; and in X of the silsesquioxane derivative represented by formula (2), when all of m, n, p, q and r are 0, a sum: 1+s is an integer from 4 or more: and
evaluation method 1
a cured film each having a thickness of 2.5 to 6 micrometers and composed of the resin composition is formed on a 50 micrometer-thick polyethylene terephthalate (PET) film base material on which an easy-adhesive layer may be formed;
the resulting PET with the cured film is cut into a lattice of 15 cm×15 cm, and the resulting square is allowed to stand with the cured film upward under an atmosphere of 25° C. and 50% RH for 24 hours or more, and then each height of the cured film lifted on four corners on a horizontal table is measured, and a mean value of the total of heights is taken as a measured value (unit: mm); and
a case of curling downward (U shape) is taken as a positive value, and a case of curling upward (inverted U shape) is taken as a negative value:
evaluation method 2
a cured film each having a thickness of 2.5 to 6 micrometers and composed of the resin composition is formed on a 50 micrometer-thick polyethylene terephthalate (PET) film base material on which an easy-adhesive layer may be formed;
on the resulting PET with the cured film, in accordance with ASTM D3359 (Method B),
an adhesion test is performed by using a crosscut adhesion method with 25 lattice patterns at a spacing of 1 millimeter; and then the PET with the cured film after performing the adhesion test is put into a constant temperature and humidity chamber at 85° C. and 85% RH for 120 hours, and then the resulting material is took out therefrom, and in accordance with ASTM D3359 (Method B),
an adhesion test is performed by using a crosscut adhesion method with 25 lattice patterns at a spacing of 1 millimeter; and evaluation criteria are as described below:
5B: 0% in percent area removed;
4B: less than 5% in percent area removed;
3B: 5% or more and less than 15% in percent area removed;
2B: 15% or more and less than 35% in percent area removed;
1B: 35% or more and less than 65% in percent area removed; and
0B: 65% or more in percent area removed.

### Claim 14 (depends on 12)

An electronic component, including the cured film according to claim 12.