CN112480682A - Addition-curable silicone composition, cured product thereof, sheet, and optical element - Google Patents
Addition-curable silicone composition, cured product thereof, sheet, and optical element Download PDFInfo
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- CN112480682A CN112480682A CN202010953506.XA CN202010953506A CN112480682A CN 112480682 A CN112480682 A CN 112480682A CN 202010953506 A CN202010953506 A CN 202010953506A CN 112480682 A CN112480682 A CN 112480682A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2383/04—Polysiloxanes
- C08J2383/07—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2483/04—Polysiloxanes
- C08J2483/05—Polysiloxanes containing silicon bound to hydrogen
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
- C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
The invention provides an addition curing type organic silicon composition which can give a cured product with excellent bending resistance. The addition-curable silicone composition contains: (A) an organic polymer represented by the following average composition formula (1)Siloxane, R1 n(C6H5)mSiO(4‑n‑m)/2(1) In the formula, R1Is a monovalent hydrocarbon radical, alkoxy or hydroxy radical, all R10.1 to 80 mol% of (a) is an alkenyl group; (B) a linear organopolysiloxane having in one molecule at least 2 (meth) acrylic groups and at least 1 silicon atom-bonded phenyl group; (C) an organohydrogenpolysiloxane represented by the following average composition formula (2) and containing at least 2 silicon atom-bonded hydrogen atoms in one molecule, R2 aHbSiO(4‑a‑b)/2(2) In the formula, R2Is a monovalent hydrocarbon group other than an aliphatically unsaturated hydrocarbon group; and (D) a catalyst for hydrosilylation.
Description
Technical Field
The present invention relates to an addition-curable silicone composition, a cured product thereof, and a sheet and an optical element using the cured product.
Background
Silicone resins are widely known as resins having excellent heat and cold resistance, electrical insulation properties, weather resistance, water resistance, transparency, and the like, and are used in various fields such as electric and electronic devices, OA devices, automobiles, precision devices, and building materials.
In recent years, in particular, in the field of LEDs, as optical elements are miniaturized or light sources are made to have higher brightness, organic materials are exposed to high temperatures and high light levels for a long period of time, and therefore, it is desired to develop a transparent organic resin having excellent heat resistance and light resistance, and silicone resins have been confirmed to have better performance than other organic resin materials in terms of properties such that they are not easily discolored and are not easily physically deteriorated in addition to excellent heat resistance and transparency, and their use as optical element materials has been expanding.
Among the silicone resins, the addition reaction curable silicone resin composition disclosed in patent document 1 is solvent-free, has good moldability compared with a solvent-based condensation curable silicone varnish (silicone varnish) and the like, and contains almost no solvent, and thus has advantages such as being mild to the environment. The silicone resin composition forms a resin with high hardness and high transparency after curing, and is also used as a composition for key tops (key tops) because of its good moldability. Patent document 2 discloses a high-hardness material which is excellent as a protective material, a covering material, and a sealing material for optical semiconductor elements such as optical couplers and light-emitting diodes, by combining a linear organopolysiloxane and a branched organopolysiloxane each having an alkenyl group directly bonded to a silicon atom, and an organohydrogenpolysiloxane. Further, patent document 3 discloses a material having high hardness and high adhesiveness by optimizing a branched organopolysiloxane, an organohydrogenpolysiloxane, and a thickener.
However, these high-hardness and high-transparency silicone resins have a disadvantage that they are easily broken when a thin sheet processed from a silicone resin monomer is bent, although they are excellent in scratch resistance and crack resistance.
Documents of the prior art
Patent document
Patent document 1: japanese patent No. 3344286
Patent document 2: japanese patent laid-open publication No. 2004-143361
Patent document 3: japanese patent laid-open publication No. 2011-
Disclosure of Invention
Technical problem to be solved by the invention
The present invention has been made in view of the above circumstances, and an object thereof is to provide an addition-curable silicone composition that gives a cured product having excellent bending resistance.
Means for solving the problems
In order to solve the above-mentioned problems, the present invention provides an addition-curable silicone composition comprising:
(A) an organopolysiloxane represented by the following average compositional formula (1),
R1 n(C6H5)mSiO(4-n-m)/2 (1)
in the formula, R1Is the same or different unsubstituted or substituted monovalent hydrocarbon, alkoxy or hydroxy group except the unsubstituted phenyl group, all R10.1 to 80 mol% of (a) is an alkenyl group, n and m are positive numbers satisfying 0.1. ltoreq. n < 0.8, 0.2. ltoreq. m < 1.9, 1. ltoreq. n + m < 2, and 0.20. ltoreq. m/(n + m) < 0.95;
(B) a linear organopolysiloxane having in one molecule at least 2 (meth) acrylic groups and at least 1 silicon atom-bonded phenyl group;
(C) an organohydrogenpolysiloxane represented by the average composition formula (2) and containing at least 2 silicon atom-bonded hydrogen atoms in one molecule, wherein the ratio of the number of silicon atom-bonded hydrogen atoms in the component (C) to the number of aliphatic unsaturated hydrocarbon groups in the components (A) and (B) is 0.01 to 0.5,
R2 aHbSiO(4-a-b)/2 (2)
in the formula, R2Is a monovalent hydrocarbon group which is the same or different species, other than the aliphatically unsaturated hydrocarbon group, substituted or unsubstituted, excluding epoxy group substitution and alkoxy group substitution, a and b being positive numbers satisfying 0.7. ltoreq. a.ltoreq.2.7, 0.01. ltoreq. b.ltoreq.1.0, and 0.8. ltoreq. a + b.ltoreq.3.0; and
(D) a hydrosilylation reaction catalyst.
Such an addition-curable silicone composition of the present invention can provide a cured product having excellent bending resistance.
In this case, the component (B) is preferably a linear organopolysiloxane represented by the following formula (3).
Wherein p is a positive number of 1 to 1,000, q is a positive number of 1 to 100, r is 2 or 3, and the arrangement of the siloxane units with parentheses is arbitrary.
Such an addition-curable silicone composition can provide a cured product having further excellent bending resistance.
Among them, more preferably, q/(p + q) in the formula (3) is 0.25 to 1.
Such an addition-curable silicone composition can provide a cured product having further excellent bending resistance.
Further, it is preferable that the addition-curable silicone composition further contains (E) an organic peroxide.
Since the component (E) has the action of promoting the polymerization of the (meth) acrylic group of the component (B) and improving the hardness of the cured product, such an addition-curable silicone composition can give a cured product with higher hardness without impairing flexibility.
The present invention also provides a cured silicone product which is a cured product of the addition-curable silicone composition.
Such a cured silicone product of the present invention has sufficient hardness and excellent bending resistance.
The present invention also provides a sheet comprising the cured silicone material. Preferably, when the sheet is bent with a thickness of 0.2mm, the radius of curvature at which cracks are generated is less than 1.5 mm.
Such a sheet of the present invention has sufficient hardness and excellent bending resistance. Therefore, even when a thin sheet processed from the silicone resin monomer is bent, the sheet is not easily broken.
The present invention also provides an optical element comprising the silicone cured product or the sheet.
The optical element of the present invention has sufficient hardness and excellent bending resistance, and is therefore suitable for applications requiring flexibility.
Effects of the invention
The addition-curable silicone composition of the present invention can give a cured product having sufficient hardness and excellent bending resistance. Therefore, the cured product is useful as an optical element, particularly as a surface layer material for a flexible substrate or a flexible panel.
Detailed Description
The present inventors have conducted extensive studies to solve the above-mentioned problems, and as a result, have found that the above-mentioned problems can be solved by a specific silicone composition, and have completed the present invention.
That is, the present invention is an addition-curable silicone composition containing the following components (a) to (D):
(A) an organopolysiloxane represented by the following average compositional formula (1),
R1 n(C6H5)mSiO(4-n-m)/2 (1)
in the formula, R1Is the same or different unsubstituted or substituted monovalent hydrocarbon, alkoxy or hydroxy group except the unsubstituted phenyl group, all R10.1 to 80 mol% of (a) is alkenyl, n andm is a positive number satisfying 0.1. ltoreq. n < 0.8, 0.2. ltoreq. m < 1.9, 1. ltoreq. n + m < 2, and 0.20. ltoreq. m/(n + m) 0.95;
(B) a linear organopolysiloxane having in one molecule at least 2 (meth) acrylic groups and at least 1 silicon atom-bonded phenyl group;
(C) an organohydrogenpolysiloxane represented by the average composition formula (2) and containing at least 2 silicon atom-bonded hydrogen atoms in one molecule, wherein the ratio of the number of silicon atom-bonded hydrogen atoms in the component (C) to the number of aliphatic unsaturated hydrocarbon groups in the components (A) and (B) is 0.01 to 0.5,
R2 aHbSiO(4-a-b)/2 (2)
in the formula, R2Is a monovalent hydrocarbon group which is the same or different species, other than the aliphatically unsaturated hydrocarbon group, substituted or unsubstituted, excluding epoxy group substitution and alkoxy group substitution, a and b being positive numbers satisfying 0.7. ltoreq. a.ltoreq.2.7, 0.01. ltoreq. b.ltoreq.1.0, and 0.8. ltoreq. a + b.ltoreq.3.0; and
(D) a hydrosilylation reaction catalyst.
The present invention will be described in detail below, but the present invention is not limited thereto.
[ addition-curable Silicone composition ]
The addition-curable silicone composition of the present invention contains the components (a) to (D) described below. Further, if necessary, other components such as (E) an organic peroxide, an addition reaction-controlling agent, and an adhesion-improving agent may be contained.
Hereinafter, each component will be described in detail.
[ (A) component ]
(A) The component (A) is an organopolysiloxane represented by the following average composition formula (1).
R1 n(C6H5)mSiO(4-n-m)/2 (1)
In the formula, R1Is the same or different unsubstituted or substituted monovalent hydrocarbon, alkoxy or hydroxy group except the unsubstituted phenyl group, all R10.1 to 80 mol% of (a) is an alkenyl group, n and m are 0.1. ltoreq. n < 0A positive number of m is more than or equal to 0.2 and less than 1.9, n + m is more than or equal to 1 and less than 2, and m/(n + m) is more than or equal to 0.20 and less than or equal to 0.95.
(A) The component (C) is preferably a liquid or solid having a viscosity of 10,000 mPas or more at 25 ℃ as measured by a rotational viscometer, and more preferably a liquid or solid having a viscosity of 100,000 to 10,000,000 mPas. When the component (A) is used, the cured product has better mechanical properties.
It is found that the average composition formula (1) is such that n + m is 1.0. ltoreq. n + m is less than 2.0, and that the component (A) contains at least R in the molecule1SiO3/2Unit, (C)6H5)SiO3/2Unit, SiO4/2One or more branched or three-dimensional network structures in the unit.
R1The radicals of (a) are of the same or different species except C6H5Substituted or unsubstituted monovalent hydrocarbon group other than the above-mentioned groups, alkoxy group or hydroxyl group. Examples of the monovalent hydrocarbon group include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, tert-butyl and hexyl, saturated hydrocarbon groups such as cycloalkyl groups such as cyclohexyl, aryl groups other than phenyl groups such as tolyl, xylyl and naphthyl, aralkyl groups such as benzyl and phenylethyl, unsaturated hydrocarbon groups such as alkenyl groups such as vinyl, allyl, propenyl, isopropenyl and butenyl, and halogenated hydrocarbon groups such as 3,3, 3-trifluoropropyl.
Wherein R is other than alkenyl1Preferably methyl, and as alkenyl, preferably vinyl.
Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.
Furthermore, R10.1 to 80% of the total number of (A) is alkenyl group, preferably 0.5 to 50% is alkenyl group. If the number of alkenyl groups is less than 0.1%, the cured product cannot have the desired hardness, and if it exceeds 80%, the cured product (silicone resin) becomes brittle because of too many crosslinking points.
For n and m, n is more than or equal to 0.1 and less than 0.8, m is more than or equal to 0.2 and less than 1.9, and n + m is more than or equal to 1 and less than 2.0. When n + m is less than 1 and when n + m is 2 or more, the desired hardness and strength may not be obtained.
Further, m/(n + m) is 0.20. ltoreq.m/(n + m) 0.95, preferably 0.30. ltoreq.m/(n + m) 0.80, and if the number of phenyl groups is outside this range, mechanical properties of the cured product may not be obtained, and transparency may be poor.
(A) The component (B) can be obtained by a known method of subjecting an alkoxysilane, a chlorosilane or the like to hydrolytic condensation, and may contain an alkoxy group or a silanol group as required.
Specific examples of the component (A) include components represented by the following formulae.
[(CH3)(CH2＝CH)SiO]6.2[(C6H5)2SiO]2.5[(C6H5)SiO3/2]7
(A) The components can be used singly or in combination of two or more.
[ (B) component ]
(B) The component (A) is a linear organopolysiloxane having at least 2 (meth) acrylic groups and at least 1 silicon atom-bonded phenyl group in one molecule.
In the present invention, (meth) acrylic group means acrylic group or methacrylic group. Examples of the (meth) acrylic group-containing group include an acryloyloxy group, a methacryloyloxy group, an acryloyloxyalkyl group, a methacryloyloxyalkyl group, an acryloyloxyalkyloxy group, a methacryloyloxyalkyloxy group and the like.
The number of carbon atoms of the alkyl (alkylene) moiety contained in these groups is not particularly limited, but is preferably 1 to 10, more preferably 1 to 5, and further preferably 2 or 3.
Among them, from the viewpoint of facilitating the hydrosilylation reaction, an acrylic group is preferable, and as the group containing an acrylic group, 2- (acryloyloxy) ethoxy group and 3- (acryloyloxy) propoxy group are more preferable.
The position of the (meth) acrylic group in the molecule is not limited, and it is preferably provided at the end of the linear organopolysiloxane, from the viewpoint of improving the flexibility of the cured product.
Examples of the organic group bonded to a silicon atom other than the (meth) acrylic group-containing group and the phenyl group in the component (B) include substituted or unsubstituted monovalent hydrocarbon groups such as alkyl groups including methyl, ethyl, propyl, and butyl, and halogenated alkyl groups including chloromethyl, 3-chloropropyl, and 3,3, 3-trifluoropropyl, and particularly preferably methyl.
(B) The viscosity of the component (C) at 25 ℃ is not particularly limited, but is preferably within a range of 10 to 1,000,000 mPas, and particularly preferably within a range of 100 to 10,000 mPas. When the viscosity is within the range of 10 to 1,000,000 mPas, the mechanical properties of the obtained cured product are not reduced, the solubility with the component (A) is good, and the cured product obtained by heat curing the composition is not clouded and the workability is not reduced. The viscosity is measured by a rotational viscometer.
As an example of the method for producing the component (B),
by [1] subjecting an organopolysiloxane having an alkenyl group bonded to a silicon atom to a hydrosilylation reaction with dimethylchlorosilane,
[2] the composition obtained in [1] is reacted with a hydroxyalkyl (meth) acrylate such as 2-hydroxyethyl acrylate in the presence of triethylamine.
Preferred examples of the component (B) include organopolysiloxanes represented by the following formula (3).
Wherein p is a positive number of 1 to 1,000, q is a positive number of 1 to 100, r is 2 or 3, and the arrangement of the siloxane units with parentheses is arbitrary.
Wherein q/(p + q) is preferably 0.25 to 1, more preferably 0.3 to 1.
Specific examples of the component (B) include those represented by the following formulae.
In the formula, the arrangement of the siloxane units with parentheses may be arbitrary.
(B) The components can be used singly or in combination.
The amount of the component (B) is preferably 1 to 100 parts by mass, more preferably 10 to 80 parts by mass, and still more preferably 20 to 60 parts by mass, based on 100 parts by mass of the component (A).
[ (C) ingredient ]
(C) The component (A) is an organohydrogenpolysiloxane represented by the following average composition formula (2) and containing at least 2 (usually 2 to 200), preferably 2 to 20 silicon atom-bonded hydrogen atoms (i.e., SiH groups) in one molecule.
R2 aHbSiO[(4-a-b)/2] (2)
In the formula, R2Is a monovalent hydrocarbon group which is the same or different species, excluding the aliphatically unsaturated hydrocarbon group, substituted or unsubstituted, excluding epoxy group substitution and alkoxy group substitution, a and b being positive numbers satisfying 0.7. ltoreq. a.ltoreq.2.7, 0.01. ltoreq. b.ltoreq.1.0, and 0.8. ltoreq. a + b.ltoreq.3.0.
(C) The organohydrogenpolysiloxane of component (a) functions as a crosslinking agent which crosslinks the alkenyl groups in component (a) by a hydrosilylation reaction, and also functions as a reactive diluent which is adjusted to a viscosity suitable for the application by diluting the composition as the case may be.
(C) The organohydrogenpolysiloxane of component (a) may have any molecular structure of linear, cyclic, branched, and three-dimensional network structures. Further, the Si-H group may be located at the molecular chain end or the non-molecular chain terminal portion, or may be located at the molecular chain end or the non-molecular chain terminal portion.
(C) The content of SiH groups per unit mass of the component (A) is preferably in the range of 0.001-0.02 mol/g, more preferably 0.004-0.017 mol/g.
R2The monovalent hydrocarbon group is an unsubstituted or substituted monovalent hydrocarbon group other than the aliphatic unsaturated hydrocarbon group, the substitution is not including epoxy group substitution and alkoxy group substitution, and examples thereof include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, tert-butyl and hexyl, saturated hydrocarbon groups such as cycloalkyl groups such as cyclohexyl, aryl groups such as phenyl, tolyl, xylyl and naphthyl, aralkyl groups such as benzyl and phenylethyl, and 3,3,3-And halogenated hydrocarbon groups such as trifluoropropyl groups, preferably alkyl groups having 1 to 12 carbon atoms, particularly 1 to 8 carbon atoms, and aryl groups having 6 to 12 carbon atoms, and particularly preferably methyl groups or phenyl groups.
Further, the number of phenyl groups relative to R is preferred2The total amount of (A) is 10-60%.
The viscosity of the component (C) at 25 ℃ is preferably 1,000 mPas or less, more preferably 3 to 100 mPas, from the viewpoint of the handling properties of the composition and the mechanical properties of the cured product. The viscosity is measured by a rotational viscometer.
Examples of the component (C) include organohydrogenpolysiloxanes represented by the following formulae.
In the formula, R2As defined above, e is an integer of 2 to 100, f is an integer of 2 to 100, and g is an integer of 1 to 30. The arrangement of the siloxane units with brackets can be arbitrary.
Specific examples of the component (C) include organohydrogenpolysiloxanes represented by the following formulae.
In the formula, the arrangement of the siloxane units with parentheses may be arbitrary.
(C) The components can be used singly or in combination.
(C) The amount of the component (B) is such that the ratio of the number of SiH groups in the component (C) to the number of aliphatic unsaturated hydrocarbon groups in the components (A) and (B), i.e., the total number of alkenyl groups and (meth) acrylic acid groups, is 0.01 to 0.5, preferably 0.05 to 0.5, and more preferably 0.2 to 0.4. If the amount is less than 0.01, the curing may be insufficient, and if the amount is more than 0.5, the bending resistance of the cured product may be poor.
[ (D) component ]
(D) The hydrosilylation reaction catalyst of the component (a) may be any catalyst as long as it is known as a catalyst having an action of promoting the hydrosilylation reaction, and a platinum group metal catalyst, a rhodium catalyst, or a palladium catalyst may be used as a representative catalyst. Chloroplatinic acid and its modifications are commonly used. Particularly in the case of electronic applications, low-chlorine catalysts are preferred, for example, a platinum compound catalyst modified with divinyltetramethyldisiloxane or divinyldiphenyldimethyldisiloxane, from which chlorine components have been removed, is preferably used.
(D) The amount of the component (C) added is only required to be an effective amount as a catalyst, and is preferably 100ppm or less (usually 0.1 to 100ppm), and particularly preferably 50ppm or less (for example, 0.5 to 50ppm), based on the total mass of the components (a), (B) and (C), based on the mass of the metal contained in the catalyst, from the viewpoints of curability and suppression of coloration due to the metal.
[ (E) ingredient ]
The addition-curable silicone composition of the invention may further contain (E) an organic peroxide. This component has the effect of accelerating the polymerization of the (meth) acrylic group of the component (B) and improving the hardness of the cured product. This can provide a cured product having higher hardness without impairing flexibility.
Specific examples of the organic peroxide include diacyl peroxides, peroxyesters, dialkyl peroxides, peroxydicarbonates, peroxyketals, hydroperoxides, and peroxysilanes.
Examples of the diacyl peroxide include isobutyl peroxide, bis (2, 4-dichlorobenzoyl) peroxide, (3,5, 5-trimethylhexanoyl) peroxide, octanoyl peroxide, dilauroyl peroxide, stearoyl peroxide, succinyl peroxide, benzoyltoluene peroxide (Benzoyl peroxide), and Benzoyl peroxide.
Examples of the peroxy ester include cumyl peroxyneodecanoate, 1,3, 3-tetramethylbutyl peroxyneodecanoate, 1-cyclohexyl-1-methylethyl peroxyneodecanoate, tert-hexyl peroxyneodecanoate, tert-butyl peroxypivalate, 1,3, 3-tetramethylbutyl peroxy2-ethylhexanoate, 2, 5-dimethyl-2, 5-bis (2-ethylhexanoate-peroxy) hexane, 1-cyclohexyl-1-methylethyl peroxy2-ethylhexanoate, tert-hexyl peroxy2-ethylhexanoate, tert-butyl peroxyisobutyrate, tert-hexyl peroxyisopropyl monocarbonate, tert-butylperoxy-3, 5, 5-trimethylhexanoate, tert-butyl peroxyisopropyl monocarbonate, tert-butyl peroxy3, 5, 5-trimethylhexanoate, and mixtures thereof, Tert-butyl peroxylaurate, 2, 5-dimethyl-2, 5-bis (m-toluoylperoxy) hexane, tert-butylperoxyisopropyl formate, tert-butylperoxy-2-ethylhexyl monocarbonate, tert-hexyl peroxybenzoate, tert-butyl peroxyacetate, and di (tert-butylperoxy) hexahydroterephthalate.
Examples of the dialkyl peroxide include α, α' -bis (tert-butylperoxy) diisopropylbenzene, dicumyl peroxide, 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane, and tert-butylcumyl peroxide.
Examples of the peroxydicarbonate include di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, di-2-ethoxymethoxy peroxydicarbonate, di (2-ethylhexyl) peroxydicarbonate, dimethoxybutyl peroxydicarbonate and di (3-methyl-3-methoxybutyl peroxy) dicarbonate.
Examples of the peroxyketal include 1, 6-bis- (t-butylperoxy-carbonyloxy) hexane, 1-bis (t-hexylperoxy) -3,3, 5-trimethylcyclohexane, 1-bis (t-hexylperoxy) cyclohexane, 1-bis (t-butylperoxy) -3,3, 5-trimethylcyclohexane, 1- (t-butylperoxy) cyclododecane and 2, 2-bis (t-butylperoxy) decane.
Examples of the hydroperoxide include diisopropylbenzene hydroperoxide and cumene hydroperoxide.
Examples of the peroxy silane include trimethylbutylperoxysilane, bis (t-butyl) dimethylperoxysilane, t-butyltrivinylperoxysilane, bis (t-butyl) divinylperoxy silane, tri (t-butyl) vinylperoxysilane, t-butyltriallyl peroxy silane, bis (t-butyl) diallylperoxysilane and tri (t-butyl) allylperoxy silane.
(E) The components can be used singly or in combination.
The amount of component (E) is preferably in the range of 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, per 100 parts by mass of component (B).
[ other ingredients ]
In addition to the components (a) to (E), other components exemplified below may be blended in the addition-curable silicone composition of the present invention as needed.
Addition reaction control agent:
an addition reaction-controlling agent may be blended in the addition-curable silicone composition of the present invention for the purpose of ensuring pot life. The addition reaction control agent is not particularly limited as long as it is a compound having a curing-inhibiting effect on the hydrosilylation catalyst of the component (D), and conventionally known addition reaction control agents can be used. Specific examples of the addition reaction control agent include phosphorus-containing compounds such as triphenylphosphine; nitrogen-containing compounds such as tributylamine, tetramethylethylenediamine, and benzotriazole; a sulfur-containing compound; acetylene compounds such as acetylene alcohols (e.g., 1-ethynylcyclohexanol and 3, 5-dimethyl-1-hexyn-3-ol); a hydrogen peroxide compound; maleic acid derivatives, and the like.
Adhesion improver:
as the adhesion improver, preferred are: an organopolysiloxane or organosilane compound having at least 1, preferably 2 or more, alkoxy groups bonded to silicon atoms in one molecule, or an organopolysiloxane or organosilane compound containing a group having an epoxy site.
Other additives:
further, an inorganic filler such as fumed silica for improving hardness may be blended according to the requirement of transparency, and a wavelength adjusting agent, a dye, a flame retardant, a heat resistant agent, an antioxidant deterioration agent, and the like may be added as necessary.
[ Silicone cured product ]
By molding and curing the addition-curable silicone composition of the present invention, a silicone cured product (silicone resin cured product) can be obtained. The molding method is not particularly limited, and press molding with a metal mold is particularly preferable.
The addition-curable silicone composition of the present invention is cured at room temperature or by heating, and heating is preferred for rapid curing. The curing conditions are not particularly limited, and vary depending on the shape of the molded product, the curing method, and the like, but the curing temperature is preferably 80 to 200 ℃, more preferably 100 to 180 ℃, and the curing time is preferably 1 minute to 24 hours, more preferably 5 minutes to 5 hours.
The hardness of the silicone cured product of the present invention is preferably 25 or more in Durometer type D (Durometer type D). Such a silicone cured product has sufficient hardness for applications requiring bending resistance, such as optical elements including a surface layer material of a flexible substrate or a flexible panel.
[ sheet ]
The silicone cured product of the present invention can be molded into a sheet form to obtain a sheet having excellent bending resistance. The bending resistance of the sheet of the present invention is preferably less than 1.5mm in the radius of curvature at which cracks are generated when the sheet is bent with a thickness of 0.2 mm.
The sheet has sufficient hardness and excellent bending resistance. Therefore, even when a thin sheet processed from the silicone resin monomer is bent, the sheet is not easily broken.
[ optical element ]
The silicone cured product or the sheet can be suitably used for an optical element.
The silicone cured product or the sheet of the present invention has sufficient hardness and excellent bending resistance, and is therefore useful as an optical element, particularly as a surface layer material for a flexible substrate or a flexible panel.
Accordingly, the optical element of the present invention has sufficient hardness and excellent bending resistance, and is therefore suitable for applications requiring flexibility.
Examples
The present invention will be specifically described below by way of examples and comparative examples, but the present invention is not limited to the following examples.
The compounds of the respective components used in the examples are as follows.
(A) The components:
a solid organopolysiloxane having an average structure represented by the following formula (1') obtained by cohydrolysis of phenyltrichlorosilane, diphenyldichlorosilane, and methylvinyldichlorosilane and dehydration condensation using potassium hydroxide.
[(CH3)(CH2＝CH)SiO]6.2[(C6H5)2SiO]2.5[(C6H5)SiO3/2]7 (1’)
(B) The components:
an organosiloxane having an average structure represented by the following formula
In the formula, the arrangement of the siloxane units with parentheses is not determined.
(C) The components:
(C-1) an organohydrogenpolysiloxane having an average structure represented by the following formula
In the formula, the arrangement of the siloxane units with parentheses is not determined.
(C-2) an organohydrogenpolysiloxane having an average structure represented by the following formula
(D) The components:
dimethyldiphenylsilicone oil solution of chloroplatinic acid (platinum content: 1% by mass)
(E) The components:
1, 6-bis (t-butylperoxycarbonyloxy) hexane (Kayaku Akzo Corporation, Kayalene 6-70)
Examples 1 to 4 and comparative examples 1 to 3
The components (a) to (E) were mixed in the blending amounts (parts by mass) shown in table 1 to prepare addition-curable silicone compositions. The value of [ Si — H ]/[ aliphatic unsaturated hydrocarbon group ] (hereinafter also referred to as "SiH ratio") is calculated as a ratio of the number of SiH groups in the component (C) to the number of aliphatic unsaturated hydrocarbon groups in the components (a) and (B), that is, the total number of alkenyl groups and (meth) acrylic groups.
< production and evaluation of cured sheet >
The addition-curable silicone compositions obtained in examples 1 to 4 and comparative examples 1 to 3 were cured by heating at 150 ℃ for 1 hour using a metal mold to produce colorless and transparent sheets having a thickness of 2mm and 0.2 mm. The following evaluations were performed on the obtained sheet, and the results are shown in table 2.
[ hardness ]
A test piece obtained by stacking 3 sheets having a thickness of 2mm was measured according to JIS K6253-3: 2012, hardness was measured using a type D durometer.
[ bending test ]
A sheet of 30mm × 70mm was bent along an axis having a diameter of 3mm (radius of curvature of 1.5mm) with sides of 30mm aligned, and the state at this time was evaluated in good (bent without breakage) and good (breakage). If the film is bent without cracking, the radius of curvature indicating the occurrence of cracks is less than 1.5 mm. The evaluation was carried out on a 2mm thick sheet and a 0.2mm thick sheet.
[ Table 1]
[ Table 2]
As is clear from tables 1 and 2, the cured products obtained by curing the addition-curable silicone compositions of examples 1 to 4 have better bending resistance than the cured products of comparative example 1 of the present invention or comparative examples 2 and 3 containing no component (B) and have a higher SiH ratio, and can be applied to flexible substrates.
Further, the addition-curable silicone compositions of examples 3 and 4 containing an organic peroxide gave cured products with higher hardness without impairing flexibility.
The present invention is not limited to the above embodiments. The above-described embodiments are merely illustrative, and any embodiments having substantially the same configuration as the inventive concept described in the claims of the present invention and exhibiting the same operational effects are included in the technical scope of the present invention.
Claims (12)
1. An addition-curable silicone composition characterized by containing:
(A) an organopolysiloxane represented by the following average compositional formula (1),
R1 n(C6H5)mSiO(4-n-m)/2 (1)
in the formula, R1Is the same or different unsubstituted or substituted monovalent hydrocarbon, alkoxy or hydroxy group except the unsubstituted phenyl group, all R10.1 to 80 mol% of (a) is an alkenyl group, n and m are positive numbers satisfying 0.1. ltoreq. n < 0.8, 0.2. ltoreq. m < 1.9, 1. ltoreq. n + m < 2, and 0.20. ltoreq. m/(n + m) < 0.95;
(B) a linear organopolysiloxane having in one molecule at least 2 (meth) acrylic groups and at least 1 silicon atom-bonded phenyl group;
(C) an organohydrogenpolysiloxane represented by the average composition formula (2) and containing at least 2 silicon atom-bonded hydrogen atoms in one molecule, wherein the ratio of the number of silicon atom-bonded hydrogen atoms in the component (C) to the number of aliphatic unsaturated hydrocarbon groups in the components (A) and (B) is 0.01 to 0.5,
R2 aHbSiO(4-a-b)/2 (2)
in the formula, R2Is a monovalent hydrocarbon group which is the same or different species, other than the aliphatically unsaturated hydrocarbon group, substituted or unsubstituted, excluding epoxy group substitution and alkoxy group substitution, a and b being positive numbers satisfying 0.7. ltoreq. a.ltoreq.2.7, 0.01. ltoreq. b.ltoreq.1.0, and 0.8. ltoreq. a + b.ltoreq.3.0; and
(D) a hydrosilylation reaction catalyst.
2. The addition-curable silicone composition according to claim 1, wherein component (B) is a linear organopolysiloxane represented by the following formula (3),
wherein p is a positive number of 1 to 1,000, q is a positive number of 1 to 100, r is 2 or 3, and the arrangement of the siloxane units with parentheses is arbitrary.
3. The addition-curable silicone composition according to claim 2, wherein q/(p + q) in formula (3) is 0.25 to 1.
4. The addition-curable silicone composition according to claim 1, further comprising (E) an organic peroxide.
5. The addition-curable silicone composition according to claim 2, further comprising (E) an organic peroxide.
6. The addition-curable silicone composition according to claim 3, further comprising (E) an organic peroxide.
7. A cured silicone product which is a cured product of the addition curable silicone composition according to any one of claims 1 to 6.
8. A sheet comprising the cured silicone according to claim 7.
9. A sheet according to claim 8, wherein the radius of curvature at which cracks occur is less than 1.5mm when bending is carried out at a thickness of 0.2 mm.
10. An optical element comprising the silicone cured product according to claim 7.
11. An optical element characterized by having the sheet of claim 8.
12. An optical element characterized by having the sheet material according to claim 9.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007246894A (en) * | 2006-02-20 | 2007-09-27 | Shin Etsu Chem Co Ltd | Heat-curable silicone composition |
| CN103224709A (en) * | 2012-01-31 | 2013-07-31 | 信越化学工业株式会社 | Curable organopolysiolxane composition, optical device sealing material, and optical device |
| CN106062080A (en) * | 2014-03-12 | 2016-10-26 | 横滨橡胶株式会社 | Curable resin composition |
| CN109749459A (en) * | 2017-11-02 | 2019-05-14 | 信越化学工业株式会社 | Addition curable silicon composition, solidfied material, optical element |
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| JP2009185226A (en) * | 2008-02-08 | 2009-08-20 | Shin Etsu Chem Co Ltd | Heat curable silicone composition and molded product using the same for optical member |
| JP2011254009A (en) * | 2010-06-03 | 2011-12-15 | Shin Etsu Chem Co Ltd | Solar cell module silicone resin composition and solar cell module |
| JP5609846B2 (en) * | 2010-11-12 | 2014-10-22 | 信越化学工業株式会社 | Addition-curing silicone adhesive composition |
| KR102560796B1 (en) * | 2017-09-29 | 2023-07-28 | 신에쓰 가가꾸 고교 가부시끼가이샤 | UV-curable silicone pressure-sensitive adhesive composition and cured product thereof |
| JP6962290B2 (en) * | 2018-08-02 | 2021-11-05 | 信越化学工業株式会社 | UV curable silicone composition for stereolithography and its cured product |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007246894A (en) * | 2006-02-20 | 2007-09-27 | Shin Etsu Chem Co Ltd | Heat-curable silicone composition |
| CN103224709A (en) * | 2012-01-31 | 2013-07-31 | 信越化学工业株式会社 | Curable organopolysiolxane composition, optical device sealing material, and optical device |
| CN106062080A (en) * | 2014-03-12 | 2016-10-26 | 横滨橡胶株式会社 | Curable resin composition |
| CN109749459A (en) * | 2017-11-02 | 2019-05-14 | 信越化学工业株式会社 | Addition curable silicon composition, solidfied material, optical element |
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| TW202116926A (en) | 2021-05-01 |
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