KR20220090432A - Photocurable silicone resin composition, silicone resin molded body obtained by curing same and method for manufacturing said molded body - Google Patents

Abstract

(Project) The present invention provides a photo-curable silicone resin composition capable of obtaining a molded article excellent in high pencil hardness, scratch resistance and flex resistance, and a silicone resin molded article as a three-dimensional crosslinked body obtained by curing the same.
(Solution) A reactive silicone resin (A) and -R ³ -CR ⁴ =CH ₂ or -CR ⁴ =CH ₂ in one molecule [provided that R ³ is an alkylene group, an alkylidene group, or -OC(=O) a polyfunctional alkylene oxide-modified unsaturated compound (B) containing at least two unsaturated groups represented by [, wherein R ⁴ represents a hydrogen atom or an alkyl group] A polyfunctional unsaturated compound (C) containing two or more unsaturated groups of silicone resin composition.

Description

A photocurable silicone resin composition, a silicone resin molded body obtained by curing the same, and a manufacturing method of the molded body TECHNICAL FIELD

The present invention relates to a photo-curable silicone resin composition capable of obtaining a molded article excellent in high pencil hardness, scratch resistance, and flex resistance, and a silicone resin molded article as a three-dimensional crosslinked body obtained by curing the same.

In recent years, in all fields, such as displays, mobile devices, home appliances, and automobile parts, the demand for designability, weight reduction, and thickness reduction is increasing. etc are being used. However, plastics and some lightweight metals have a low surface hardness and have a problem that scratches easily occur. Then, the method of forming the hard-coat layer which protects the surface is used.

For such a hard coat layer, many acrylic compositions are used. Since the acrylic composition is generally formed and cured by a radical reaction by irradiation with active energy rays such as ultraviolet rays or electron beams, it can be cured in a short time and at low temperatures, and toughness can be maintained by the resin composition to be blended. , adhesives, etc. are widely used.

As an example of such a hard-coat layer, the present inventors paid attention to the reactive silicone resin which has a cage structure and has a reactive functional group, and has been examining, Reactivity in the reactive silicone resin which has this cage structure By increasing the number of functional groups and blending it with an unsaturated compound capable of radical copolymerization in a specific ratio, it is possible to provide a transparent silicone resin molded body with excellent balance of high surface hardness, heat resistance, mechanical properties and dimensional stability. What can be used suitably as an alternative use of inorganic glass is disclosed (patent documents 1-2). Moreover, about the manufacturing method of the reactive silicone resin which has such a cage structure, patent document 3 is specifically disclosed.

However, with respect to such a silicone resin composition, although it is high surface hardness, there exists a subject that cracks and peeling are produced at the time of bending.

Japanese Patent No. 4558643 Japanese Patent No. 5698566 Japanese Laid-Open Patent Publication No. 2004-143449

An object of the present invention is to provide a photo-curable silicone resin composition capable of obtaining a molded article excellent in high pencil hardness, scratch resistance and flex resistance, and a silicone resin molded article which is a three-dimensional crosslinked body obtained by curing the same.

The present inventors find out that the said subject is solved by containing the polymeric compound which has a specific structure as a radically polymerizable unsaturated compound in the composition in a specific ratio with respect to such a photocurable silicone resin composition especially in the composition, reached

That is, the present invention relates to a reactive silicone resin (A) and -R ³ -CR ⁴ =CH ₂ or -CR ⁴ =CH ₂ [provided that R ³ is an alkylene group, an alkylidene group, or -OC(= A polyfunctional alkylene oxide-modified unsaturated compound (B) containing at least two unsaturated groups represented by [O)- group and R ⁴ represents a hydrogen atom or an alkyl group and further having an alkylene oxide-modified moiety (B), and 1 molecule A polyfunctional unsaturated compound (C) containing two or more of the unsaturated groups described above and not containing an alkylene oxide-modified moiety is blended in a mass ratio of 1-50:10-40:10-80, characterized in that It is a photocurable silicone resin composition.

ADVANTAGE OF THE INVENTION According to this invention, the photocurable silicone resin composition which can obtain the molded object excellent in high pencil hardness, abrasion resistance, and bending resistance, and the silicone resin molded object which is a three-dimensional crosslinked body obtained by hardening this can be provided.

Hereinafter, each element constituting the present invention will be described in detail, but the following description is an example of an embodiment of the present invention, and the present invention is limited to the following description unless it departs from the gist of the present invention not. In addition, when the expression "-" is used in this specification, it shall be used as an expression including the numerical value or physical property value before and behind it. In addition, in this invention, when the expression "(meth)acryl" is used, one or both of "acryl" and "methacryl" are meant. It is the same also about "(meth)acrylate" and "(meth)acryloyl."

The photo-curable silicone resin composition of the present invention comprises a reactive silicone resin (A) and -R ³ -CR ⁴ =CH ₂ or -CR ⁴ =CH ₂ [provided that R ³ is an alkylene group, an alkylidene group or A polyfunctional alkylene oxide-modified unsaturated compound (B) comprising at least two unsaturated groups represented by -OC(=O)- and R ⁴ represents a hydrogen atom or an alkyl group] and further having an alkylene oxide-modified moiety (B) and a polyfunctional unsaturated compound (C) containing two or more of the above unsaturated groups in one molecule and not containing an alkylene oxide modified site in a mass ratio of 1-50:10-40:10-80 characterized in that

It is preferable to mix|blend this reactive silicone resin (A) used by this invention in the mass ratio of 1-50 with respect to 100 mass parts of photocurable silicone resin compositions, More preferably, it is a mass ratio of 2.5-30. When it is less than 1 mass part, a crosslinking density will fall and it will become soft, and abrasion resistance and pencil hardness will deteriorate. When it is more than 50 mass parts, a crosslinking density rises, becomes hard and becomes brittle, and cracks and peeling are caused at the time of bending|flexion.

As the reactive silicone resin (A), a known silicone resin can be used, and as a preferred embodiment, it is represented by the following general formula (1), and is polyorganosilsesquioxane (basket-type polyorgan) having a cage structure in its structural unit. It is also called nosylsesquioxane (polyorganosilsesquioxane is also called silsesquioxane) as the main component. In general formula (1), R is an organic functional group which has a (meth)acryloyl group, and n is 8, 10 or 12.

[RSiO _3/2 ] _n (1)

In general formula (1), R is an organic functional group which has a (meth)acryloyl group, and n is 8, 10 or 12. As an organic functional group which has a (meth)acryloyl group, group represented by the following general formula (4) is mentioned. In general formula (4), m is an integer of 1-3, and R< ¹ > is a hydrogen atom or a methyl group.

CH ₂ =CR ¹ -COO-(CH ₂ ) _m - (4)

Such a reactive silicone resin has an organic functional group which has a (meth)acryloyl group on the silicon atom in a molecule|numerator. As a specific structure of cage polyorganosilsesquioxane in which n is 8, 10, and 12 in general formula (1), cage structures as shown in the following structural formulas (5), (6) and (7), respectively, can be heard In addition, R in the following formula represents the same thing as R in General formula (1).

[Formula 1]

Here, such a reactive silicone resin can be manufactured by the method described in said patent document 3 etc. For example, it can be obtained by partially condensing the silicon compound represented by RSiX ₃ in the presence of a polar solvent and a basic catalyst, followed by a partial condensation, and further recondensing the obtained hydrolysis product in the presence of a non-polar solvent and a basic catalyst. Here, R is an organic functional group which has a (meth)acryloyl group, it is group specifically represented by the said General formula (4), and X represents a hydrolysable group. If the specific example of preferable R is shown, 3-methacryloxypropyl group, methacryloxymethyl group, and 3-acryloxypropyl group will be illustrated.

The hydrolysable group X will not be specifically limited if it is group which has hydrolysability, Although an alkoxyl group, an acetoxy group, etc. are mentioned, It is preferable that it is an alkoxyl group. Examples of the alkoxyl group include a methoxy group, an ethoxy group, an n- or i-propoxy group, or an n-, i- or t-butoxy group. A methoxy group is preferable because of its high reactivity.

Preferred compounds among the silicon compounds represented by RSiX ₃ are methacryloxymethyltriethoxysilane, methacryloxymethyltrimethoxysilane, 3-methacryloxypropyltrichlorosilane, and 3-methacryloxypropyltrimethoxysilane. , 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, and 3-acryloxypropyltrichlorosilane are mentioned. Especially, it is preferable to use 3-methacryloxypropyl trimethoxysilane with an easy acquisition of a raw material.

Examples of the basic catalyst used in the hydrolysis reaction include alkali metal hydroxides such as potassium hydroxide, sodium hydroxide and cesium hydroxide, or tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, and benzyltrimethylammonium. and ammonium hydroxide salts such as hydroxide and benzyltriethylammonium hydroxide. Among these, tetramethylammonium hydroxide is used preferably from a point with high catalytic activity. A basic catalyst is normally used as aqueous solution.

About hydrolysis reaction conditions, 0-60 degreeC is preferable and, as for reaction temperature, 20-40 degreeC is more preferable. When the reaction temperature is lower than 0°C, the reaction rate is slowed, the hydrolyzable group remains in an unreacted state, resulting in consumption of a large amount of reaction time. On the other hand, if it is higher than 60° C., since the reaction rate is too fast, a complicated condensation reaction proceeds, and as a result, high molecular weight of the hydrolysis product is promoted. In addition, the reaction time is preferably 2 hours or more. When the reaction time is less than 2 hours, the hydrolysis reaction does not proceed sufficiently, and there is a possibility that the hydrolyzable group remains in an unreacted state.

The hydrolysis reaction requires the presence of water, which may be supplied from an aqueous solution of a basic catalyst or may be added as separate water. The amount of water is preferably not less than an amount sufficient to hydrolyze the hydrolyzable group, preferably 1.0 to 1.5 times the theoretical amount. In addition, it is necessary to use an organic polar solvent at the time of hydrolysis, and alcohol, such as methanol, ethanol, 2-propanol, or another organic polar solvent can be used as an organic polar solvent. Preferably, it is water and C1-C6 soluble lower alcohol, and it is more preferable to use 2-propanol. When a non-polar solvent is used, a reaction system does not become uniform, a hydrolysis reaction does not fully advance, unreacted hydrolysable group remains, and it is unpreferable.

After completion of the hydrolysis reaction, water or a water-containing reaction solvent is separated. Separation of water or a water-containing reaction solvent can be carried out by means such as evaporation under reduced pressure. In order to sufficiently remove moisture and other impurities, a non-polar solvent is added to dissolve the hydrolysis reaction product, the solution is washed with saline, etc., and then dried with a drying agent such as anhydrous magnesium sulfate. can If the non-polar solvent is separated by evaporation or other means, the hydrolysis reaction product can be recovered. However, if the non-polar solvent can be used as a non-polar solvent used in the next reaction, there is no need to separate it.

In a hydrolysis reaction, a condensation reaction of a hydrolyzate arises with hydrolysis. The hydrolysis product accompanying the condensation reaction of a hydrolyzate turns into a colorless viscous liquid with a number average molecular weight of 1400-5000 normally. Although the hydrolysis product varies depending on the reaction conditions, it becomes an oligomer having a number average molecular weight of 1400 to 3000, and most, preferably approximately all, of the hydrolyzable groups X are substituted with OH groups, and most of the OH groups, preferably 95% or more is condensed. Regarding the structure of the hydrolysis product, there are multiple types of cage, ladder, and random silsesquioxanes, and even for compounds that have cage structures, the ratio of the complete cage structure is small, and a part of the basket is open. An imperfect basket-like structure is the main factor. Therefore, the silsesquioxane of cage structure is selectively manufactured by condensing the siloxane bond by heating the hydrolysis product obtained by this hydrolysis in the presence of a basic catalyst in an organic solvent further (referred to as recondensation).

Specifically, it is carried out as follows. That is, after the completion of the hydrolysis reaction as described above, after the water or the water-containing reaction solvent is separated, the recondensation reaction is carried out in the presence of a non-polar solvent and a basic catalyst. About the reaction conditions of a recondensation reaction, the range of 100-200 degreeC is preferable and, as for reaction temperature, 110-140 degreeC is more preferable. In addition, when the reaction temperature is too low, sufficient driving force is not obtained to cause the recondensation reaction, and the reaction does not proceed. Since there is a possibility that a (meth)acryloyl group may raise|generate a self-polymerization reaction when reaction temperature is too high, it is necessary to suppress reaction temperature, or to add a polymerization inhibitor etc. The reaction time is preferably 2 to 12 hours. The amount of the non-polar solvent used is preferably an amount sufficient to dissolve the hydrolysis reaction product, and the amount of the basic catalyst used is preferably in the range of 0.1 to 10 mass% (wt%) with respect to the hydrolysis reaction product.

As a non-polar solvent, what is necessary is just to be a thing with no water solubility, or a thing with little, but a hydrocarbon type solvent is preferable. Examples of the hydrocarbon-based solvent include a non-polar solvent having a low boiling point, such as toluene, benzene, and xylene. Among them, it is preferable to use toluene. Moreover, as a basic catalyst, the basic catalyst used for the said hydrolysis reaction can be used, Alkali metal hydroxides, such as potassium hydroxide, sodium hydroxide, cesium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, Although ammonium hydroxide salts, such as tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, and benzyltriethylammonium hydroxide, are mentioned, A catalyst soluble in nonpolar solvents, such as tetraalkylammonium, is preferable.

In addition, although it is preferable to use the hydrolyzed product used for recondensation by washing with water and dehydration, and using what was concentrated, it can be used even if water washing and dehydration are not performed. At the time of this reaction, although water may be present, it is not necessary to add it actively, and it is preferable to stay at about the water|moisture content carried in from the basic catalyst solution. In addition, when hydrolysis of a hydrolysis product is not fully performed, although the water|moisture content more than the theoretical amount required for hydrolyzing the hydrolysable group which remain|survives is required, a hydrolysis reaction is fully implemented normally. After the recondensation reaction, the catalyst is removed by washing with water and concentrated to obtain a silsesquioxane mixture. As for the obtained silsesquioxane mixture, Preferably, the number of silicon atoms in a molecule|numerator and the number of (meth)acryloyl groups are equivalent.

Although the silsesquioxane mixture obtained in this way differs with reaction conditions and the state of a hydrolysis product, as for a structural component, 70% or more of multiple types cage-shaped silsesquioxane is the whole, and the remainder is ladder type and random It is thought to be a crosslinked silsesquioxane. Since these are difficult to separate and take much time, in this invention, when using cage silsesquioxane represented by General formula (1), 70% or more of multiple types cage silsesquioxane contain It is preferable to use the silsesquioxane which does. Moreover, there is no difference in the effect obtained as cage silsesquioxane content is 70 % or more. As for the structural component of multiple types of cage silsesquioxane, T8 represented by General formula (5) is 20-40 %, T10 represented by General formula (6) is 40-50 %, Other components are General formula (7) ) is T12 represented by . T8 can be separated by precipitating the silsesquioxane mixture as needle-like crystals by leaving the mixture at 20°C or lower. In addition, about the content rate of cage silsesquioxane, it can confirm using GPC, LC-MS, etc., for example.

Such a reactive silicone resin may be a mixture of T8 to T12, and one or two such as T8 may be separated or concentrated therefrom, but is not limited to the reactive silicone resin obtained by the above manufacturing method.

The polyfunctional alkylene oxide-modified unsaturated compound (B) is in the molecule -R ³ -CR ⁴ =CH ₂ or -CR ⁴ =CH ₂ [provided that R ³ is an alkylene group, an alkylidene group, or -OC(=O) - group, and R< ⁴ > represents a hydrogen atom or an alkyl group] contains at least 2 unsaturated groups and has an alkylene oxide modified site|part. Here, it is preferable that it is ethylene oxide or a propylene oxide about this alkylene oxide modified site|part. Moreover, it is preferable to include at least one alkylene oxide modified site|part with respect to one said unsaturated group. By containing (B) component, the crack and peeling at the time of a bending|flexion can be suppressed, maintaining high surface hardness.

It is preferable to mix|blend the polyfunctional alkylene oxide modified unsaturated compound (B) in a mass ratio of 10-40 with respect to 100 mass parts of photocurable silicone resin compositions, More preferably, it is a mass ratio of 10-30. When it is less than 10 parts by mass, sufficient flexibility cannot be imparted, cracks and peeling occur at the time of bending, and when more than 40 parts by mass, the surface hardness decreases, which causes a decrease in pencil hardness and scratch resistance.

Examples of the polyfunctional alkylene oxide-modified unsaturated compound (B) include alkylene oxide-modified glycerin tri(meth)acrylate, alkylene oxide-modified diglycerin tetra(meth)acrylate, and alkylene oxide-modified dipentaerythritol. Tetra(meth)acrylate, alkylene oxide modified dipentaerythritol hexa(meth)acrylate, polyethylene glycol acrylate, polypropylene glycol acrylate, etc. are mentioned. In addition, you may use these (B) components individually or in combination of 2 or more types.

Specifically, 3 moles of ethylene oxide modified trimethylolpropane triacrylate, 6 moles of ethylene oxide modified trimethylolpropane triacrylate, 9 moles of ethylene oxide modified trimethylolpropane triacrylate, and 3 moles of propylene oxide modified trimethylolpropane triacrylate Rate, ethylene oxide 4 moles modified pentaerythritol tetraacrylate, ethylene oxide 5 moles modified pentaerythritol tetraacrylate, ethylene oxide 6 moles modified dipentaerythritol hexaacrylate, ethylene oxide 12 moles modified dipentaerythritol hexaacrylic Rate, 3 moles of ethylene oxide modified glycerin triacrylate, 3 moles of propylene oxide modified glycerin triacrylate, 4 moles of ethylene oxide modified diglycerin tetraacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, 3 moles of ethylene oxide Modified bisphenol A diacrylate, 4 moles of ethylene oxide modified bisphenol A diacrylate, 10 moles of ethylene oxide modified bisphenol A diacrylate, 4 moles of ethylene oxide modified bisphenol F diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate Acrylates etc. are mentioned. Among these compounds, it is more preferable to have three or more photopolymerizable unsaturated groups from the viewpoint of surface hardness, and from the viewpoint of suppressing cracking and peeling during bending, at least one alkylene oxide moiety is included for each unsaturated group It is preferable that it is a polyfunctional alkylene oxide modified unsaturated compound to do.

The polyfunctional unsaturated compound (C) which does not contain an alkylene oxide modified site|part is -R ³ -CR ⁴ =CH ₂ or -CR ⁴ =CH ₂ [provided that R ³ is an alkylene group, an alkylidene group or - OC(=O)- represents a group, and R ⁴ represents a hydrogen atom or an alkyl group], preferably at least two unsaturated groups, more preferably 100% by mass of component (C) Among them, 20 mass% or more is a polyfunctional unsaturated compound containing a hydroxyl group.

As for the polyfunctional unsaturated compound (C) which does not contain an alkylene oxide modified site|part, the mass ratio of 10-80 is preferable with respect to 100 mass parts of photocurable silicone resin compositions, More preferably, it is a mass ratio of 30-80. When it is less than 10 mass parts, crosslinking will become inadequate and abrasion resistance and pencil hardness will deteriorate. When it is more than 80 mass parts, a crosslinking density will rise and it will become hard and brittle, and a crack or peeling will arise at the time of bending.

The polyfunctional unsaturated compound (C) which does not contain an alkylene oxide modified site|part, Preferably, 10-100 mass % of the polyfunctional unsaturated compound which has the said unsaturated group 2 or more or 3 or more is included. By mix|blending such a polyfunctional unsaturated compound, the molded object of high surface hardness can be obtained.

As an unsaturated compound containing a hydroxyl group among the said polyfunctional unsaturated compounds, pentaerythritol triacrylate, glycerol dimethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol tetraacrylate, etc. can be illustrated. Since these have a hydroxyl group in the molecule, the radical generated by the reduction of the distance between molecules by the interaction of the hydroxyl group rapidly reacts with the double bond, thereby improving the curing rate, and radical polymerization proceeds before the reaction between oxygen and radical From this, it becomes possible to suppress the curing inhibition by oxygen.

As described above, the polyfunctional unsaturated compound (C) containing no alkylene oxide-modified moiety to be blended in the present silicone resin composition is preferably an unsaturated compound containing a hydroxyl group in an amount of 20 mass% or more, more preferably It is preferable that 30 mass % or more of (C) is an unsaturated compound containing a hydroxyl group. In this range, intermolecular interaction is effective. Although there is no upper limit in particular of mixing|blending, when it exceeds 60 mass %, the raise of the oxygen inhibition inhibitory effect will almost lose|eliminate.

On the other hand, as a polyfunctional unsaturated compound which does not contain a hydroxyl group, trimethylol propane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, etc. can be illustrated. In addition to these, all of the terminal hydroxyl groups of the skeleton obtained by modifying some or all of the hydroxyl groups of pentaerythritol and dipentaerythritol with glycols such as ethylene and isopropylene, γ-butyrolactone, etc. R ³ -CR ⁴ =CH ₂ or -CR ⁴ =CH ₂ [provided that R ³ represents an alkylene group, an alkylidene group or a -OC(=O)- group, and R ⁴ represents a hydrogen atom or an alkyl group] A compound modified with an unsaturated group can also be used. Or urethane acrylate, acrylic copolymer acrylate, etc. can be illustrated. In addition, these polyfunctional unsaturated compounds, the unsaturated compound which do not contain a hydroxyl group, etc. may be used individually, respectively, and may mix and use 2 or more types.

Moreover, you may mix|blend with the polyfunctional unsaturated compound (C) which does not contain the said alkylene oxide modified site|part, a reactive monofunctional or other bifunctional monomer (unsaturated compound) in the range which does not reduce surface hardness. Examples of the monofunctional monomer include styrene, vinyl acetate, N-vinylpyrrolidone, butyl acrylate, 2-ethylhexyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, n-decyl acrylate, isobornyl acrylic rate, dicyclopentenyloxyethyl acrylate, phenoxyethyl acrylate, trifluoroethyl methacrylate, and the like can be exemplified. Examples of other bifunctional monomers include tripropylene glycol diacrylate, 1,6-hexanediol diacrylate, bisphenol A diglycidyl ether diacrylate, tetraethylene glycol diacrylate, and neopentyl glycol dihydroxypivalate. Acrylates etc. can be illustrated.

It is preferable that a monofunctional monomer and another bifunctional monomer are contained in the polyfunctional unsaturated compound (C) which does not contain an alkylene oxide modified|denatured site|part at 20 mass % or less, More preferably, it is 10 mass % or less. When it mix|blends more than 20 mass %, since surface hardness tends to fall, it is unpreferable.

It is preferable that the photocurable silicone resin composition of this invention contains an active energy ray polymerization initiator (D) further. Active energy ray polymerization initiator (D) is 0.1-20 mass parts with respect to 100 mass parts of photocurable silicone resin compositions, Preferably it is 1-10 mass parts. When it does not reach this range, it will be suppressed that bridge|crosslinking, abrasion resistance, and pencil hardness deteriorate. Conversely, even if it contains exceeding this range, there exists a possibility that the improvement of the further reaction rate cannot be expected.

As an active energy ray polymerization initiator (D), the compound of a benzoin type, an acetophenone type, an anthraquinone type, a thioxanthone type, a ketal type, and a phosphine oxide type can be used preferably, for example. Moreover, the photoinitiation adjuvant and photosensitizer which exhibit an effect in combination with a photoinitiator can also be used.

As a specific active energy ray polymerization initiator (D), As a photoinitiator, Benzoin types, such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin isobutyl ether; Acetophenone, 2,2-diethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropane-1 acetophenones such as -one, diethoxyacetophenone, 1-hydroxycyclohexylphenyl ketone, and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one; anthraquinones such as 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-chloroanthraquinone, and 2-amylanthraquinone; thioxanthone such as 2,4-diethyl thioxanthone, 2-isopropyl thioxanthone, and 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenones such as benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, and 4,4'-bismethylaminobenzophenone; Phosphine oxides, such as 2,4,6- trimethylbenzoyl diphenylphosphine oxide and bis(2,4,6- trimethylbenzoyl)-phenylphosphine oxide, etc. are mentioned. These can be used individually or as a mixture of 2 or more types, Furthermore, tertiary amines, such as triethanolamine and methyldiethanolamine, N,N- dimethylaminobenzoic acid ethyl ester, N,N- dimethylaminobenzoic acid isoamyl It can be used in combination with a photoinitiation adjuvant, such as benzoic acid derivatives, such as an ester, etc.

Examples of the photosensitizer include 1,4-dimethoxynaphthalene, 1,4-diethoxynaphthalene, 1,4-di(n-propoxy)naphthalene, 1,4-di(i-propoxy)naphthalene, 2,6 -Naphthalene type, such as dimethoxynaphthalene, 2,6- diethoxy naphthalene, 2,6- di(n-propoxy) naphthalene, 2,6- di(i-propoxy) naphthalene, benzophenone, 4-methylbenzo Benzophenone systems, such as phenone, 4-(methylphenylthio) phenyl]-phenylmethane, and 4,4'-bis (diethylamino) benzophenone, are mentioned preferably. As a compounding quantity, it is the range of 0.05-3 mass parts with respect to a photocurable silicone resin composition from a viewpoint of photocurability and transparency, Preferably it is the range of 0.1-3 mass parts. If it is less than 0.05 mass part, the improvement effect of a sensitizer is not exhibited, but the expected hardness improvement effect is not acquired. Moreover, since it exists in the tendency for coloring to become strong when it exceeds 3 mass parts, it is preferable to use within the said range. In order to adjust photocurability and transparency, you may combine several photosensitizers.

The photocurable silicone resin molded article of the present invention can be produced by curing the photocurable silicone resin composition by irradiating the photocurable silicone resin composition with active energy rays such as visible rays, ultraviolet rays, or electron beams, preferably ultraviolet rays having a wavelength of 10 to 400 nm. However, by irradiating visible light with a wavelength of 400 to 700 nm, a cured molded article can be obtained. Although the wavelength in particular of the light to be used is not restrict|limited, In particular, near-ultraviolet rays with a wavelength of 200-400 nm are used preferably. Examples of the lamp used as the ultraviolet ray generator include a low-pressure mercury lamp (output: 0.4 to 4 W/cm), a high-pressure mercury lamp (40 to 160 W/cm), an ultra-high pressure mercury lamp (173 to 435 W/cm), and a metal halide lamp. (80-160 W/cm) etc. can be illustrated.

As a method of obtaining a molded product (silicone resin copolymer or cured product) by irradiation with active energy rays such as light irradiation, either under an oxygen barrier atmosphere or an atmospheric atmosphere may be used, but the composition of the present invention may be polymerization cured under an atmospheric atmosphere From the viewpoint of providing a good molded article, it is preferably carried out in an atmospheric atmosphere. For example, by injecting the photo-curable silicone resin composition of the present invention into a mold having an arbitrary cavity shape and made of a transparent material such as quartz glass, irradiating ultraviolet rays with an ultraviolet lamp to carry out polymerization curing, and demolding from the mold In the case of not using a mold or a method for manufacturing a molded article having a desired shape, for example, a doctor blade or a roll-shaped coater is used on a moving steel belt to apply the photo-curable silicone resin composition of the present invention, and an ultraviolet lamp The method of manufacturing a sheet-like molded object, etc. can be illustrated by carrying out polymerization and hardening by furnace.

The shape of the molded object is arbitrary, and a film, a coating film, etc. may be sufficient. This molded object is obtained by radical copolymerizing the photocurable silicone resin composition of this invention, and hardening it. The molded article or cured product of the present invention is a three-dimensionally crosslinked polymer, and in this case, the same molding and curing method as that of the thermosetting resin can be employed.

In addition, various types of polycarbonate (PC), polymethyl methacrylate (PMMA), polyethylene terephthalate (PET), triacetyl cellulose (TAC), transparent polyimide (CPI), polyimide (PI), metal plate, glass, etc. A method of forming a molded article as a hard coat film on the surface of a substrate can be exemplified by applying the photocurable silicone resin composition of the present invention to a substrate, or by diluting and applying the photocurable silicone resin composition of the present invention with various organic solvents and curing it. Specifically, the casting method, the roller coat method, the bar coat method, the spray coat method, the air knife coat method, the spin coat method, the flow coat method, the curtain coat method, and the dipping method are mentioned. In addition, a coating film thickness considers the formation film thickness after drying and hardening by an ultraviolet lamp, and adjusts it according to solid content concentration. When the organic solvent is used for adjustment of solid content concentration, it is preferable to remove the organic solvent by drying etc. after application|coating. The drying temperature is set as conditions under which the base material to be used does not deform, and the drying time is preferably 1 hour or less from the viewpoint of productivity. Moreover, from a viewpoint of abrasion resistance and adhesiveness, the thickness of a hard-coat film is 0.5-100 micrometers, Preferably it is 1-60 micrometers.

Specific examples of the organic solvent include aromatic organic solvents such as toluene and xylene, ketone organic solvents such as methyl ethyl ketone and methyl isobutyl ketone, ethyl acetate, n-propyl acetate, isopropyl acetate, isobutyl acetate, and the like. ester organic solvents, alcohol-based organic solvents such as methanol, ethanol, n-propanol, isopropanol, and n-butanol, and glycol ether-based organic solvents such as propylene glycol monomethyl ether, known organic solvents can be used. In particular, it is preferable to include a glycol-based organic solvent.

Examples of the glycol ether-based organic solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol n-propyl ether, ethylene glycol monoisopropyl ether, ethylene Glycol dipropyl ether, ethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, ethylene glycol dibutyl ether, ethylene glycol isoamyl ether, ethylene glycol monohexyl ether, ethylene glycol mono 2-ethylhexyl ether, methoxyethoxy ethylene glycol ethers such as ethanol and ethylene glycol monoallyl ether; propylene glycols such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, butoxypropanol; , among these, propylene glycol monomethyl ether is preferable.

The laminate (photocurable silicone resin laminate) obtained in this way comprising the resin molded product of the present invention has a pencil hardness (according to JIS K 5600) of 2H or more, preferably 3H or more, and has abrasion resistance of steel wool test As a result, it is desirable that at least 1,500 g load and 300 reciprocation will not cause scratches. In addition, as for bending resistance, for a test piece of 80 x 50 mm in width and length, with the layer of this silicone resin molded body on the outside, an acrylic cylinder having a diameter of 50 mm was wound so that the long side of the rectangle follows the circumference of the cylinder. At this time, it is preferable not to generate a crack or peeling of this silicone resin molded object.

Various additives can be added to the photocurable silicone resin composition of this invention in the range which does not deviate from the objective of this invention. Various additives as organic/inorganic fillers, plasticizers, flame retardants, heat stabilizers, antioxidants, light stabilizers, ultraviolet absorbers, leveling agents, slip properties imparting agents, antistatic agents, mold release agents, foaming agents, nucleating agents, colorants, optical brighteners, crosslinking agents, dispersing agents adjuvant, a resin component, etc. can be illustrated.

Example

Hereinafter, the Example of this invention is shown. In addition, the reactive silicone resin used in the following examples was obtained by the method shown in the following synthesis example.

[Synthesis Example 1]

In a reaction vessel equipped with a stirrer, a dropping funnel, and a thermometer, 40 ml of 2-propanol (IPA) as a solvent and a 5% aqueous solution of tetramethylammonium hydroxide (aqueous TMAH solution) were charged as a basic catalyst. 15 ml of IPA and 12.69 g of 3-methacryloxypropyltrimethoxysilane (MTMS: SZ-6030 manufactured by Toray Dow Corning Silicon Co., Ltd.) were placed in a dropping funnel, and the IPA solution of MTMS was stirred at room temperature while stirring the reaction vessel. It was dripped over 30 minutes. After completion of the MTMS dripping, the mixture was stirred for 2 hours without heating. After stirring for 2 hours, the solvent was removed under reduced pressure, and the mixture was dissolved in 50 ml of toluene. The reaction solution was washed with saturated brine until neutral, and then dehydrated over anhydrous magnesium sulfate. Anhydrous magnesium sulfate was separated by filtration and concentrated to obtain 25.8 g of a hydrolysis product (silsesquioxane). This silsesquioxane was a colorless, viscous liquid soluble in various organic solvents.

Next, 20.65 g of silsesquioxane obtained above, 82 ml of toluene, and 3.0 g of a 10% TMAH aqueous solution were placed in a reaction vessel equipped with a stirrer, Dean Stark, and a cooling tube, and the mixture was gradually heated to evaporate water. Further, by heating to 130 °C, toluene was recondensed at a reflux temperature. The temperature of the reaction solution at this time was 108 degreeC. After refluxing to toluene and stirring for 2 hours, the reaction was terminated. The reaction solution was washed with saturated brine until neutral, and then dehydrated over anhydrous magnesium sulfate. Anhydrous magnesium sulfate was filtered off and concentrated to obtain 18.77 g of cage silsesquioxane (mixture) as the target product. The obtained cage silsesquioxane (S1) was a colorless viscous liquid soluble in various organic solvents.

As a result of performing mass spectrometry after liquid chromatography separation of the reactant after the recondensation reaction, in the molecular structures of the above structural formulas (5), (6) and (7), where R is a methacryloyl group, ammonium ion is attached to Molecular ions are confirmed, and the composition ratio is T8:T10:T12:others about 2:4:1:3, and it can be confirmed that it is a silicone resin having a cage structure as a main component. In addition, T8, T10, and T12 correspond to what made R a methacryloyl group in Formulas (5), (6), and (7), respectively.

[Example 1]

Reactive silicone resin (A) cage-shaped silicone resin (S1) having on all silicon atoms the methacryloyl group of Synthesis Example 1 as component: 25 parts by mass, polyfunctional alkylene oxide-modified unsaturated compound (B) Ethylene oxide as component 12 mole modified dipentaerythritol hexaacrylate (B1) (trade name KAYARAD DPEA-12 manufactured by Nippon Kayaku Co., Ltd.): 20 parts by mass, dipentaerythritol hexaacrylate (Mw = 578.57, the number of acrylic groups = 6, the number of hydroxyl groups = 0) and dipentaerythritol pentaacrylate (Mw = 524.52, the number of acrylic groups = 5, the number of hydroxyl groups = 1) 65:35 (mass ratio) of a mixture (C1) ( Nippon Kayaku Co., Ltd. product name KAYARAD DPHA): 55 parts by mass, 1-hydroxy-cyclohexyl-phenylketone (D1) (trade name Omnirad184 manufactured by IGM) was mixed as an active energy ray polymerization initiator (D), and a photocurable silicone resin A composition was obtained.

Next, the obtained photocurable silicone resin composition: 50 parts by mass, propylene glycol monomethyl ether as a diluting solvent: 50 parts by mass, and a fluorine-based surface conditioner (KY-1203 manufactured by Shin-Etsu Chemical Co., Ltd.): 1 part by mass are mixed, and the mixture is waiting A film after drying using a bar coater on the polymethyl methacrylate side of a composite plate made of polymethyl methacrylate/polycarbonate (thickness 650 µm, length 10 cm, width 10 cm C001 manufactured by Escabo Sheet) It apply|coated so that thickness might be set to 10 micrometers, and it dried at 80 degreeC for 5 minutes. Thereafter, it was cured under an oxygen atmosphere at an accumulated exposure amount of 2,800 mJ/cm 2 to obtain a laminated body test piece formed by forming a layer of this silicone resin molded body on the polymethyl methacrylate surface of the composite plate.

[Examples 2 to 14, Comparative Examples 1 to 5]

A photocurable silicone resin composition was obtained in the same manner as in Example 1 except that the raw materials and composition ratios shown in Table 1 were used. In addition, another abbreviation in a table|surface shows the following.

DGE-4A: 4 moles of ethylene oxide modified diglycerin tetraacrylate (B2) (the number of acrylic groups = 4, the number of modified ethylene oxide = 4, manufactured by Kyoeisha Chemical)

M3130: 3 moles of ethylene oxide modified trimethylolpropane triacrylate (B3) (the number of acrylic groups = 3, the number of modified ethylene oxide = 3, manufactured by MIWON)

M3190: 9 mol of ethylene oxide modified trimethylolpropane triacrylate (B4) (the number of acrylic groups = 3, the number of modified ethylene oxide = 9, manufactured by MIWON)

M320: 3 mol of propylene oxide modified glycerin triacrylate (B5) (number of acrylic groups = 3, number of modifications of propylene oxide = 3, manufactured by MIWON)

Light acrylate PE-3A (C2): 40 of pentaerythritol tetraacrylate (the number of acrylic groups = 4, the number of hydroxyl groups = 0) and pentaerythritol triacrylate (the number of acrylic groups = 3, the number of hydroxyl groups = 1): 60 (mass ratio) mixture (manufactured by Kyoeisha Chemical)

Light acrylate TMP-A (C'1): trimethylolpropane triacrylate (number of acrylic groups = 3, number of hydroxyl groups = 0, manufactured by Kyoeisha Chemical)

[evaluation]

The following evaluation was performed using the laminated body test piece obtained above. In addition, the evaluation result was shown to Tables 1-3.

[Pencil hardness]

According to JIS K 5600, the silicone resin molded body side surface of the laminate test piece was scraped at a load of 750 g and an angle of 45 degrees using a Mitsubishi Pencil Uni, and the hardness at which scratches did not occur was visually judged.

[Scratch resistance]

Using #0000 steel wool, the silicone resin molded body side surface of the laminate test piece was abraded using a reciprocating wear tester (Type: 30S, manufactured by HEIDON) under a load of 1.5 kg/cm 2 . A flaw length of 1 mm or more was judged as a flaw, and the presence or absence of a flaw was visually observed under a fluorescent lamp, and the number of flaws was evaluated according to the following criteria.

◎: No scratches after 1,000 round trips

○: 300 round trip no scratches

△: Less than 10 scratches in 300 round trips

×: There are more than 10 scratches in 300 round trips

[Flexibility Resistance]

A laminated body test piece was cut to 80 x 50 mm in width and length, and each was wound on an acrylic cylinder having a diameter of 50 mm with the silicone resin molded body side facing the outside so that the long side of the rectangle follows the circumference of the cylinder, and the silicone Deformation and cracks of the resin molded body were visually observed.

○: No cracks or peeling occur

x: A crack or peeling generate|occur|produces

Claims (8)

a reactive silicone resin (A), and
-R ³ -CR ⁴ =CH ₂ or -CR ⁴ =CH ₂ [provided that R ³ represents an alkylene group, an alkylidene group or a -OC(=O)- group, and R ⁴ is a hydrogen atom or an alkyl group in one molecule a polyfunctional alkylene oxide-modified unsaturated compound (B) containing at least two unsaturated groups represented by ] and further having an alkylene oxide-modified site;
A polyfunctional unsaturated compound (C) containing two or more of the above unsaturated groups in one molecule and not containing an alkylene oxide modified moiety is blended in a mass ratio of 1-50:10-40:10-80. A photocurable silicone resin composition comprising The method of claim 1,
The polyfunctional alkylene oxide-modified unsaturated compound (B) is in the molecule -R ³ -CR ⁴ =CH ₂ or -CR ⁴ =CH ₂ [provided that R ³ is an alkylene group, an alkylidene group, or -OC(=O) - represents a group, and R ⁴ represents a hydrogen atom or an alkyl group] contains at least two unsaturated groups, the alkylene oxide modification site is ethylene oxide or propylene oxide, and at least one alkylene oxide modification for each unsaturated group A photocurable silicone resin composition, characterized in that it is a polyfunctional alkylene oxide-modified unsaturated compound containing a moiety. 3. The method of claim 1 or 2,
The polyfunctional unsaturated compound (C) is -R ³ -CR ⁴ =CH ₂ or -CR ⁴ =CH ₂ [provided that R ³ represents an alkylene group, an alkylidene group or a -OC(=O)- group in the molecule; R ⁴ represents a hydrogen atom or an alkyl group], and 20 mass % or more of 100 mass % of component (C) is a polyfunctional unsaturated compound containing a hydroxyl group. silicone resin composition. 4. The method according to any one of claims 1 to 3,
The reactive silicone resin (A) has the general formula (1)
[RSiO _3/2 ] _n (1)
[provided that R is an organic functional group having a (meth)acryloyl group, and n is 8, 10 or 12], wherein the structural unit contains polyorganosilsesquioxane having a cage structure as a main component A photo-curable silicone resin composition, characterized in that. 5. The method according to any one of claims 1 to 4,
Active energy ray polymerization initiator (D) is contained, The photocurable silicone resin composition characterized by the above-mentioned. A photocurable silicone resin molded article obtained by radical copolymerizing the photocurable silicone resin composition according to any one of claims 1 to 5 and curing it. The photocurable silicone resin laminated body obtained by apply|coating the photocurable silicone resin composition in any one of Claims 1-5 to a base material, making it radical copolymerize and hardening it. A method for producing a photocurable silicone resin molded article, wherein the photocurable silicone resin composition according to any one of claims 1 to 5 is subjected to radical copolymerization by irradiating an active energy ray under the atmosphere to obtain a silicone resin molded article.