JP2013234301A - Photocurable and thermosetting resin composition, molded product and article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photocurable and thermosetting resin composition suitable for a functional film material and an antifouling scratch-resistant coating material.SOLUTION: As a resin composition, a silicon compound having the following structure is used as a main component of a siloxane unit. In the structure, a linking group between a (meth)acryloxy group as a photo-polymerizable group and silicon includes a urethane bond, and 1 to 5 (meth)acryloxy groups are linked to the same silicon atom by chemical bonds excluding a siloxane bond. In this way, by using the silicon compound, a distance between crosslinking points in a cured resin is increased compared to conventional compositions to alleviate curing shrinkage while keeping sufficient hardness. The hardness and toughness of a cured product are both achieved in a high level by a secondary interaction by a hydrogen bond between structural groups in the urethane bond moiety.

Description

  The present invention relates to a light and thermosetting resin composition, a molded article comprising the light and thermosetting resin composition, and an article having a cured film of the light and thermosetting resin composition. If it is transparent, it has a linear expansion coefficient and birefringence suitable for applications such as touch panels, and it has excellent wear resistance, shape stability, and crack resistance. The present invention relates to a light and thermosetting resin composition that is transparent, high in hardness, excellent in scratch resistance, stain resistance, and crack resistance, and forms a protective film with little curing shrinkage.

  Synthetic resins such as polymethyl methacrylate resin, polycarbonate resin, polystyrene resin, cyclic polyolefin resin, polyethylene terephthalate resin, and triacetyl cellulose resin have advantages such as light weight, transparency, and easy processability. Therefore, in recent years, such synthetic resins have been used in various fields such as optical disks such as CD and DVD, display windows such as liquid crystal and EL panels, and various functional films represented by transparent conductive films for touch panels. Yes.

  However, the resin materials represented by the above have problems in lack of heat resistance, linear expansion coefficient, birefringence, etc. when used as a film substrate for touch panels, and transparent conductive films using the substrate film The same problem was inevitable. On the other hand, high heat-resistant polymers such as polyimide, polyethersulfone, polyetherketone, polyarylate, and liquid crystal polymer are generally excellent in heat resistance, chemical resistance, and electrical insulation, but are easily colored and have limited use in the optical field. Has been.

  Among these, in Japanese Patent No. 4256756 (Patent Document 1) and Japanese Patent No. 44099797 (Patent Document 2), a polysiloxane having a siloxane unit having a polymerizable group typified by an acrylic group as a main constituent unit is disclosed. A technique relating to an organosilsesquioxane and a resin composition using the organosilsesquioxane mixed with a resin is disclosed. Further, in Patent Document 2, when a polyfunctional acrylic having an alicyclic structure is used as a second essential component to obtain a cured molded product, parameters such as a coefficient of linear expansion and birefringence are effective for a touch panel member. Disclosed is a technique that can be modified to various physical properties.

  By the way, in addition to the applied technology as the molded product, in order to improve the scratch resistance of the non-silicone molded surface represented by the above, a transparent and scratch-resistant silicone (siloxane) hard coat is recorded on the medium. In general, formation on the reproduction beam incident side surface is performed. The hard coat is formed by using a compound having two or more photoreactive groups such as a vinyl group or a (meth) acryl group in the molecule, an alkoxysilane having a photoreactive group such as a vinyl group or a (meth) acryl group. A siloxane compound having a cage structure hydrolyzed and condensed in the presence of a basic catalyst (Japanese Patent Laid-Open No. 2002-363414 (Patent Document 3), Japanese Patent No. 4400571 (Patent Document 4)), an alkoxysilane having a photoreactive group And a composition containing a reaction product of colloidal silica and the like are applied to the surface of the medium and cured by irradiation with active energy rays such as ultraviolet rays. However, such a hard coat employs a (meth) acryloxypropyl group and a (meth) acryloxymethyl group as photoreactive groups, and although a certain hardness can be obtained by the balance of the functional group amount, Instead, distortion due to curing shrinkage was large, crack resistance was insufficient when the film thickness was increased, and warping as an article increased when the medium was a film. Further, the warpage of the molded product due to the same curing shrinkage is not improved in Patent Documents 1 and 2 described above.

  Also, on the surfaces of films such as optical disks, display windows, touch panels, etc., contamination with various contaminants and fingerprints occur during use. Such contamination and fingerprint adhesion are not desirable, and the surface of the optical disk (optical information medium) is subjected to appropriate surface treatment to improve antifouling properties, reduce fingerprint adhesion properties, or improve fingerprint removal properties. Sometimes. For example, various water and oil repellent treatments have been studied on the surface of optical information media.

  As an improvement in antifouling property, a siloxane compound having a cage structure obtained by hydrolytic condensation of an alkoxysilane having a polymerizable functional group and an alkoxysilane having a perfluoroalkyl group in the presence of a basic catalyst has been proposed ( Japanese Patent No. 3603133 (Patent Document 5)). A film obtained by curing a composition containing this compound has a high contact angle of oleic acid and is expected to improve antifouling properties. Wearability etc. will fall remarkably.

  Examples of applying a siloxane compound containing a (meth) acryl group as a photoreactive group as a silica-based film have been reported so far. However, this technique is not applied as a hard coating agent, but has a flatness / lowness aimed at decomposing / erasing organic groups and forming pores after curing by heating, UV / EB irradiation, and plasma treatment. It is used as an interlayer insulating film having a dielectric constant (Japanese Patent Application Laid-Open No. 2005-179587 (Patent Document 6)).

  As a silicon compound having a polyfunctional (meth) acrylic group, a corresponding polyfunctional (meth) acrylic group-containing allyl compound and hydrochlorosilane are subjected to a hydrosilylation reaction, followed by an alkoxysilylation with an alcohol (Japanese Patent Application Laid-Open No. Hei 10). -1061313 (Patent Document 7), JP 2010-229054 (Patent Document 8)), or a urethanation reaction product of a hydroxyl group-containing polyfunctional (meth) acrylate and an isocyanate silane (Patent No. 3164431) Document 9) is disclosed, but any of the applied techniques is only applied as a so-called silane coupling agent component that is not intentionally hydrolyzed by condensing the alkoxysilyl group moiety. The field is also limited, such as dental materials, the present invention The art, such as those that draw the line.

Japanese Patent No. 4256756 Japanese Patent No. 44099797 JP 2002-363414 A Japanese Patent No. 4400751 Japanese Patent No. 3603133 Japanese Patent Application Laid-Open No. 2005-179587 Japanese Patent Laid-Open No. 10-101613 JP 2010-229054 A Japanese Patent No. 3164431

  The present invention has been made in view of the above circumstances, and has a linear expansion coefficient and birefringence that are transparent as a molded product and suitable for applications such as a touch panel, and are excellent in wear resistance, shape stability, and crack resistance. A light and thermosetting resin composition which is transparent as a cured film, has high hardness and scratch resistance, has excellent resistance to contamination against contaminants such as fingerprint stains, crack resistance, and has a protective film with little curing shrinkage, It is an object of the present invention to provide a molded article using a light and thermosetting resin composition and an article having a cured film of the light and thermosetting resin composition.

In order to achieve the above object, the present invention provides the following light and thermosetting resin compositions, molded articles and articles.
[1] The following siloxane unit formula (1)
[Wherein, X is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ^{1 to} R ⁶ are substituted or unsubstituted monovalent hydrocarbon groups having 1 to 10 carbon atoms, and the substituent is fluorine. Atom, chlorine atom, bromine atom, (meth) acryloxy group, epoxy structure-containing group, mercapto group, isocyanate group, amino functional group, perfluoroalkyl group, poly (hexafluoropropylene oxide) structure-containing group, silyl group Or one or more monovalent organic groups. However, any one of R ^{1 to} R ^{6 is represented by} the following formula (2)
(Wherein R ⁷ is the following formula (3)
A is a branched or unbranched carbon group having 2 to 10 carbon atoms, and may have an oxygen atom between them, and does not contain any other hetero atom (n + 1) -valent hydrocarbon group ( R ⁸ is independently a hydrogen atom or a methyl group, m is an integer of 1 to 10, and n is an integer of 1 to 5. The CH ₂ ═CR ⁸ —COO— group may be bonded to any one or more of the carbon atoms of A. )
The number of siloxane units substituted by the organic group represented by the formula (2) with respect to the total siloxane units is 20 to 100 mol%, and a is an average of 0 ≦ a < 0.4, b is average 0 ≦ b <0.5, c is average 0 <c ≦ 1, d is average 0 ≦ d <0.4, and e is average 0 ≦ e <0.4. 0.2 and a + b + c + d = 1. ]
The light and thermosetting resin composition containing the silicone resin represented by these.
[2] The light and thermosetting resin composition according to [1], wherein m in the formula (2) is 3.
[3] The organic group represented by the formula (2) is represented by the following formulas (4) to (8).
(Wherein R ⁸ has the same meaning as described above.)
The light and thermosetting resin composition according to [2], which is any one of the structural groups represented by the formula (2) or a combination of two or more thereof.
[4] The light and thermosetting resin composition according to any one of [1] to [3], wherein the silicone resin has a weight average molecular weight of 2,000 to 50,000.
[5] The silicone resin has 0.1 to 20 mol% of siloxane units substituted with perfluoroalkyl groups or poly (hexafluoropropylene oxide) structure-containing groups with respect to the total siloxane units [1] to [4 ] The light and thermosetting resin composition in any one of.
[6] The light and thermosetting resin composition according to any one of [1] to [5], further including a polyfunctional (meth) acrylic compound.
[7] The light and thermosetting resin composition according to any one of [1] to [6], further including at least one metal oxide fine particle.
[8] The light and thermosetting resin composition according to any one of [1] to [7], further including at least one of a radical photopolymerization catalyst and a thermal condensation catalyst.
[9] A molded product obtained by curing the light and thermosetting resin composition according to any one of [1] to [8].
[10] An article formed by forming a cured film of the light and thermosetting resin composition according to any one of [1] to [8].

  According to the light and thermosetting resin composition of the present invention, a (meth) acryloxy group which is a photopolymerizable group and a silicon linking group have a urethane bond, and the same silicon atom has a chemical bond excluding a siloxane bond. When a conventionally known (meth) acryl group-containing silane coupling agent is used as a siloxane unit by using a silicon compound having a structure in which 1 to 5 (meth) acryloxy groups are linked as the main component of the siloxane unit ( Since the distance between the cross-linking points of the cured resin is longer than that in FIG. 1 (a)), the cross-linking density is reduced and the curing shrinkage is eased (FIG. 1 (b)), and shape stability is obtained as a molded product. Generation | occurrence | production of the curvature of a film article can be suppressed as a cured film. In addition, the cured product is transparent and has a linear expansion coefficient and birefringence suitable for applications such as a touch panel, and has excellent antifouling properties against contaminants such as fingerprint stains. In addition, sufficient hardness is expressed due to the nature of the polyfunctional (meth) acrylic group, and furthermore, the hardness and toughness of the cured product are made compatible at a high level by secondary interaction due to hydrogen bonding between structural groups in the urethane bond site. (FIG. 1 (c)), and a protective film excellent in crack resistance, wear resistance, and scratch resistance can be obtained.

It is explanatory drawing of the effect expression mechanism by the resin composition of this invention.

Hereinafter, the present invention will be specifically described.
The silicone resin used as the main component of the light and thermosetting resin composition of the present invention is represented by the following siloxane unit formula (1):
[Wherein, X is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ^{1 to} R ⁶ are substituted or unsubstituted monovalent hydrocarbon groups having 1 to 10 carbon atoms, and the substituent is fluorine. Atom, chlorine atom, bromine atom, (meth) acryloxy group, epoxy structure-containing group, mercapto group, isocyanate group, amino functional group, perfluoroalkyl group, poly (hexafluoropropylene oxide) structure-containing group, silyl group Or one or more monovalent organic groups. However, any one of R ^{1 to} R ^{6 is represented by} the following formula (2)
(Wherein R ⁷ is the following formula (3)
A is a branched or unbranched carbon group having 2 to 10 carbon atoms, and may have an oxygen atom between them, and does not contain any other hetero atom (n + 1) -valent hydrocarbon group ( R ⁸ is independently a hydrogen atom or a methyl group, m is an integer of 1 to 10, and n is an integer of 1 to 5. The CH ₂ ═CR ⁸ —COO— group may be bonded to any one or more of the carbon atoms of A. )
The number of siloxane units substituted by the organic group represented by the formula (2) with respect to the total siloxane units is 20 to 100 mol%, and a is an average of 0 ≦ a < 0.4, b is average 0 ≦ b <0.5, c is average 0 <c ≦ 1, d is average 0 ≦ d <0.4, and e is average 0 ≦ e <0.4. 0.2 and a + b + c + d = 1. ]
It is represented by

In the silicone resin constituting this resin composition, a, b, and d in the siloxane unit formula (1) can be 0. Therefore, (R ⁶ SiO _3/2 ) _c (OX) _e , ( R ⁶ SiO _3/2 ) _c (SiO _4/2 ) _d (OX) _e , (R ¹ R ² R ³ SiO _1/2 ) _a (R ⁶ SiO _3/2 ) _c (OX) _e , (R ⁴ R ⁵ SiO _2/2 ) _b (R ⁶ SiO _3/2 ) _c (OX) _e , (R ⁴ R ⁵ SiO _2/2 ) _b (R ⁶ SiO _3/2 ) _c (SiO _4/2 ) _d ( OX) _e , (R ¹ R ² R ³ SiO _1/2 ) _a (R ⁶ SiO _3/2 ) _c (SiO _4/2 ) _d (OX) _e , (R ¹ R ² R ³ SiO _1/2 ) there is _{^{a (R 4 R 5 SiO 2/2}} ) b (R 6 SiO 3/2) c (OX) e. This silicone resin is a branched, reticulated or three-dimensional organopolysiloxane resin composed of these siloxane units, and has a (meth) acryloxy group. Cures rapidly by energy beam irradiation or heat.

  In the siloxane unit formula (1), a, b, c and d mean the average number of moles of each siloxane unit when the total number of moles of each siloxane unit is 1, and each siloxane unit is in one molecule. It shows how many mol% is contained on average. Therefore, a + b + c + d = 1. Moreover, e has shown how many mol% of the siloxane unit which the hydrolyzable group couple | bonded on silicon is contained in each siloxane unit. Therefore, 0 ≦ e <(b + c + d).

When M units (R ¹ R ² R ³ SiO _1/2 ) are introduced into the organopolysiloxane resin, the molecular weight generally decreases, so the range is 0 ≦ a <0.4, preferably 0 ≦ a <. 0.2. When the D unit (R ⁴ R ⁵ SiO _2/2 ) is introduced, the degree of branching of the resin is reduced, the modulus of the cured product is lowered, and crack resistance and antifouling properties are improved. b <0.5, preferably 0 ≦ b <0.02 on average. When the T unit (R ⁶ SiO _3/2 ) is introduced, the degree of branching is generally improved, the modulus of the cured product is increased, and the wear resistance is improved. Therefore, the average 0 <c ≦ 1, preferably Is 0.8 ≦ c ≦ 1. When Q unit (SiO _4/2 ) is introduced, generally the degree of branching of the resin is remarkably improved, the modulus of the cured product is remarkably increased, and the crack resistance is lowered, so d is an average of 0 ≦ d < 0.4, preferably d = 0. When a siloxane unit containing a hydrolyzable group is introduced, the hardness improvement due to thermal condensation increases, but on the other hand, a reactive group remains in the resin and storage stability decreases, so e is an average. 0 ≦ e <0.2, preferably 0 ≦ e <0.1 on average.

In the siloxane unit formula (1), among R ^{1 to} R ⁶ which are substituents bonded to a silicon atom, the substituted or unsubstituted monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms includes a methyl group, Examples thereof include linear, branched or cyclic alkyl groups such as ethyl group, propyl group, butyl group, pentyl group, hexyl group and cyclohexyl group, and alkenyl groups such as vinyl group and allyl group. Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms include aryl groups such as phenyl group, tolyl group, phenylethyl group, xylyl group, and naphthyl group, and aralkyl groups. Substituents include fluorine atom, chlorine atom, bromine atom, (meth) acryloxy group, epoxy structure-containing group, mercapto group, isocyanate group, amino functional group, perfluoroalkyl group, poly (hexafluoropropylene oxide) structure-containing group And a silyl group.

Among these, the following formula (2)
(Wherein R ⁷ is the following formula (3)
A is a branched or unbranched carbon group having 2 to 10 carbon atoms, and may have an oxygen atom between them, and does not contain any other hetero atom (n + 1) -valent hydrocarbon group ( R ⁸ is independently a hydrogen atom or a methyl group, m is an integer of 1 to 10, and n is an integer of 1 to 5. The CH ₂ ═CR ⁸ —COO— group may be bonded to any one or more of the carbon atoms of A. )
At least one of R ^{1 to} R ⁶ is included (that is, at least one of the organic groups bonded to the silicon atom of the silicone resin is a group of the above formula (2)). .
R ⁸ is preferably a hydrogen atom in view of curability when irradiated with high energy rays such as ultraviolet rays. It is preferable that the siloxane unit which the organic group represented by Formula (2) substitutes with respect to a total siloxane unit is 40-99.9 mol%, More preferably, it is 70-99.7 mol%.

The alkylene group C _m H _2m in the above formula (2) adjusts the distance between the crosslinking points of the cured resin, and m is an integer of 1 to 10, preferably 1 to 8, and more preferably. M = 3. When m exceeds 10, the balance between the hardness and toughness of the cured product intended in the present invention is impaired.

  In the above formula (3), the number (n) of (meth) acryloxy groups is an integer of 1 to 5, thereby ensuring a sufficient hardness as a cured product. When n exceeds 5, the balance between the hardness and toughness of the cured product intended in the present invention is impaired.

Therefore, the organic group represented by the above formula (2) is represented by the following formulas (4) to (8).
(Wherein R ⁸ has the same meaning as described above.)
It is preferable that it is an organic group represented by.

In the siloxane unit formula (1), with respect to (O _1/2 X) bonded to a silicon atom, X is a hydrogen atom or a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, C1-C4 alkyl groups, such as i-butyl group and t-butyl group, Preferably they are a hydrogen atom and a methyl group, More preferably, it is a hydrogen atom.

In the siloxane unit formula (1), any one of R ^{1 to} R ⁶ which is a substituent bonded to a silicon atom is represented by the formula (2) in consideration of curability when irradiated with high energy rays such as ultraviolet rays. As a photoreactive group in addition to the organic group, the following formula (9)
^{_{CH 2 = C (R 9)}} COO (CH 2) l - (9)
(In the formula, R ⁹ is a hydrogen atom or a methyl group, and l is an integer of 1 to 8.)
It is good to have the organic group represented by these. R ⁹ is preferably a hydrogen atom in consideration of curability when irradiated with high energy rays such as ultraviolet rays.

  Here, when the content of the organic group-containing siloxane unit of the formula (2) is Amol% and the content of the organic group-containing siloxane unit of the formula (9) is Bmol%, 0.1 <A / (A + B) It is preferable that ≦ 1, more preferably 0.2 <A / (A + B) ≦ 1. If the content is outside the above range, the balance between imparting flexibility of the molded product due to the reduction in crosslink density, which is an effect of the present invention, and improving the hardness of the molded product due to high activity of the polymerizable group may be impaired.

  In addition, 0-80 mol% is preferable and, as for the siloxane unit which the organic group represented by the said Formula (9) has substituted, More preferably, it is 0-30 mol%.

In the siloxane unit formula (1), for the purpose of improving the antifouling effect, a siloxane unit substituted with a perfluoroalkyl group or a poly (hexafluoropropylene oxide) structure-containing group is substituted for the total siloxane unit. It is preferable that it is 0.1-20 mol%, More preferably, it is 1-5 mol%. As the perfluoroalkyl group, one in which part or all of the hydrogen atoms of the alkyl group having 1 to 10 carbon atoms are substituted with fluorine atoms, for example,
C ₄ F ₉ C ₂ H ₄ —, C ₆ F ₁₃ C ₂ H ₄ —, C ₈ F ₁₇ C ₂ H ₄ —
Etc. As poly (hexafluoropropylene oxide) structure,
C ₃ F ₇ OC (CF ₃ ) FCF ₂ OC (CF ₃ ) FCH ₂ OC ₃ H _6- ,
F (C (CF ₃ ) FCF ₂ O) ₆ C (CF ₃ ) FC (═O) NHC ₃ H ₆ −
Etc.

  In the siloxane unit formula (1), for the purpose of improving the magic ink resistance, the content of dimethylsiloxane units is preferably 0.1 to 10 mol%, more preferably 0. 1 to 3 mol%. When the content is less than the above-mentioned content, sufficient magic ink resistance cannot be obtained, and when the content is large, sufficient abrasion resistance may not be obtained.

  In addition to the siloxane unit S-1 in which the organic group represented by the formula (2) is substituted in this way, the silicone resin is a siloxane unit S-2 in which the organic group of the formula (9) is substituted. , A perfluoroalkyl group and / or a poly (hexafluoropropylene oxide) structure-containing group includes one or more of substituted siloxane units S-3 and dimethylsiloxane units S-4, the formula (2 The siloxane unit S-1 substituted by the organic group represented by) is 20 to 99.9 mol%, particularly 30 to 98.9 mol%.

(Manufacturing method of silicone resin)
The hydrolyzable silane monomer as a precursor for the siloxane unit formula (1) is not particularly limited as long as it has one or more hydrolyzable silyl groups in the molecule, but the above formulas (4) to (8) In order to obtain a structural group selected from the group consisting of the above, hydrolyzable silane monomers as exemplified in the following formulas (10) to (13) may be used.

(In the formula, Me represents a methyl group.)

Here, the exemplary compound has a hydrolyzable silyl group that is a trimethoxysilyl group, but is not limited thereto. Examples of the silyl group include a methyldimethoxysilyl group, a dimethylmethoxysilyl group, a triethoxysilyl group, and a methyldiethoxysilyl group. Or a dimethylethoxysilyl group. In the case of having two or more hydrolyzable silyl groups, those having a silyl group as a substituent among R ^{1 to} R ⁶ correspond thereto. When the silyl group as a substituent is also a hydrolyzable silyl group, a corresponding siloxane unit is simultaneously contained in the unit formula (1). Examples of hydrolyzable silane monomers having two or more hydrolyzable silyl groups include 1,2-bistrimethoxysilylethane, 1,2-bistriethoxysilylethane, 1,2-bis (methyldimethoxysilyl) ethane, 1,2 -Bis (methyldiethoxysilyl) ethane, 1,6-bis (trimethoxysilyl) hexane, 1,6-bis (triethoxysilyl) hexane, 1,8-bis (trimethoxysilyl) octane, 1,8- Bis (triethoxysilyl) octane, 1,19-bis (trimethoxysilylethyl) -permethyldecasiloxane, N, N-bis (trimethoxysilylpropyl) amine, tris- (trimethoxysilylpropyl) isocyanurate, etc. Can be mentioned. These contribute to the improvement of the magic ink wiping property.

  As an outline of the method for producing a silicone resin, a silane compound containing a hydrolyzable silyl group (alkoxy group) as described above is more water than the amount in which all alkoxy groups are hydrolyzed and condensed in the presence of a basic catalyst. (Meth) acryloxy group-containing organopolysiloxane resin can be obtained by hydrolytic condensation with.

Here, examples of the basic catalyst include sodium hydroxide, potassium hydroxide, ammonia, tetraalkylammonium hydroxide and the like. Among these, tetraalkylammonium hydroxide is preferable.
The addition amount of the basic catalyst is preferably 0.1 to 20% by mass, particularly 1 to 10% by mass, based on the silane compound and siloxane compound added.

  The amount of water used for the hydrolytic condensation is larger than the amount required for hydrolytic condensation of all the alkoxy groups of the compounded silane compound and siloxane compound. Water is 0.55 to 10 mol, preferably 0.6 to 5 mol. If it is less than 0.55 mol, hydrolysis of the alkoxy group does not proceed, and if it exceeds 10 mol, condensation does not proceed. In any case, an unreacted silane monomer remains and repelling or the like occurs on the surface of the film.

  The hydrolysis condensation reaction must be performed in alcohol, and examples of the alcohol used include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, and t-butanol.

  The above-mentioned silane compound, alcohol, and basic catalyst are blended, and water is added to proceed with hydrolysis and condensation. The reaction temperature at this time is 0-200 degreeC, Preferably it is 0-50 degreeC.

  After hydrolytic condensation, neutralize with acid or neutralize by washing with water, and then distill off alcohol, etc. to remove (meth) acryloxy group-containing organo, which is substantially free of solvents A polysiloxane resin can be obtained.

  The weight average molecular weight in terms of polystyrene by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a developing solvent for the silicone resin represented by the siloxane unit formula (1) is 2,000 to 50,000. Is more preferably 2,500 to 30,000, and particularly preferably 3,000 to 25,000. If the molecular weight is too small, condensation is insufficient, storage stability is poor, unreacted siloxane units remain, and repellency or the like may occur on the film surface. If it is too large, the viscosity becomes high and handling may be difficult.

  The resin composition containing the organopolysiloxane resin (silicone resin) represented by the siloxane unit formula (1) of the present invention may contain a polyfunctional (meth) acrylate as a reactive diluent, if necessary. preferable. When polyfunctional (meth) acrylate is not included, the organopolysiloxane resin becomes solid (crystallized) or increases in viscosity, which makes it difficult to manufacture stably and makes it very difficult to apply to substrates. There is a risk.

The polyfunctional (meth) acrylate forms a matrix of the film obtained after curing. The polyfunctional (meth) acrylate is a compound having two or more (meth) acryl groups in the molecule. For example, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, ethylene Oxide-modified bisphenol A di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol tri (meta) ) Acrylate, dicyclopentadienyl diacrylate, 3- (meth) acryloyloxyglycerin mono (meth) acrylate, urethane acrylate, epoxy acrylate, ester acrylate, etc. Including but not necessarily limited thereto.
These compounds may use only 1 type and may use 2 or more types together.

  The blending amount of the polyfunctional (meth) acrylate is preferably 0 to 100 parts by mass, particularly preferably 0 to 70 parts by mass with respect to 100 parts by mass of the silicone resin. If the amount of polyfunctional (meth) acrylate is too large, sufficient wear resistance may not be obtained. In addition, when mix | blending polyfunctional (meth) acrylate, it is preferable that it is 10 mass parts or more from the point which exhibits the effect effectively.

  By mixing an organopolysiloxane resin (silicone resin) represented by the above siloxane unit formula (1) and, if necessary, a polyfunctional (meth) acrylate coating composition and a curing catalyst, light and heat curing Can be obtained, which is cured by high energy rays such as ultraviolet rays and heat.

  Here, a radical initiator and / or a thermal condensation catalyst can be used as the curing catalyst. The radical initiator can be selected from ordinary photopolymerization initiators (radical photopolymerization catalysts) such as acetophenone, benzoin, benzophenone, and thioxanthone. For example, Darocur 1173, Irgacure 651, Irgacure 184, Irgacure 907 (all manufactured by Ciba Specialty Chemicals) and the like can be mentioned.

  In addition, the thermal condensation catalyst can be appropriately selected from known ones. Specific examples of the thermal condensation catalyst used in the present invention include lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium methylate, sodium acetate, sodium formate, n-hexylamine, tributylamine, diazabicycloundecene, etc. Basic compounds such as tetraisopropyl titanate, tetrabutyl titanate, aluminum triisobutoxide, aluminum triisopropoxide, aluminum acetylacetonate, aluminum perchlorate, aluminum chloride, cobalt octylate, cobalt acetylacetonate, zinc octylate, Metal-containing compounds such as zinc acetylacetonate, iron acetylacetonate, tin acetylacetonate, dibutyltin octylate, dibutyltin laurate, p-toluenesulfonic acid, tri Lol acidic compounds such as acetic acid, and the like.

  The blending amount of the curing catalyst can be 0.1 to 15 parts by mass with respect to 100 parts by mass of the total amount of the silicone resin and the polyfunctional (meth) acrylate. A preferable compounding amount is 0.5 to 10 parts by mass, and if it is less than 0.1 part by mass, the curability may be deteriorated.

  The coating agent composition containing the organopolysiloxane resin (silicone resin) represented by the above siloxane unit formula (1) of the present invention may further comprise a metal oxide fine particle, a silane coupling agent, a non-polymerizable agent, if necessary. Dilution solvents, polymerization inhibitors, antioxidants, ultraviolet absorbers, light stabilizers, antifoaming agents, leveling agents and the like may be included.

  Examples of the metal oxide fine particles include oxide fine particles such as Si, Ti, Al, Zn, Zr, In, Sn, and Sb, or composite oxide fine particles thereof. Moreover, you may use what coat | covered the surface with silica, an alumina, etc. Specific examples of the metal oxide fine particles include fine particles of silica, alumina, zirconia, titania and the like, and silica fine particles are preferable. By adding such metal oxide fine particles, characteristics such as wear resistance can be further enhanced.

Further, the silica fine particles may be hollow or porous which is expected to have an effect such as a low refractive index.
Among the silica fine particles, those having a surface modified with a hydrolyzable silane compound having an active energy ray reactive group are preferably used. Such reactive silica fine particles undergo a crosslinking reaction by irradiation with active energy rays when the hard coat is cured, and are fixed in the polymer matrix.
In addition, the compounding quantity of metal oxide microparticles | fine-particles, such as a silica microparticle, is 5-100 mass parts with respect to 100 mass parts of total amounts of silicone resin and polyfunctional (meth) acrylate.

  Non-polymerizable diluents include aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, alcohol solvents, ester solvents, ketone solvents, and the like. Among them, ester solvents and ketone solvents are preferable because of compatibility with silicone resins.

  The light and thermosetting resin composition of the present invention is a molding material suitable for various functional films typified by a transparent conductive film for touch panels, more specifically, a linear expansion coefficient and birefringence suitable for applications such as touch panels. And a molding material that provides a film with excellent balance between high transparency, high dimensional stability (shape stability), crack resistance and wear resistance. The light and thermosetting resin composition of the present invention is a surface of an optical information medium such as a read-only optical disc, an optical recording disc, a magneto-optical recording disc, etc. More specifically, it is applied to the surface of a recording or reproducing beam incident side, an optical lens, an optical filter, an antireflection film, and various display elements such as a liquid crystal display, a CRT display, a plasma display, an EL display, etc. By doing so, it is possible to impart an antifouling effect to the contaminants such as scratch resistance, crack resistance, fingerprint stains and the like, and wiping ability of the magic ink. An article having this cured film is excellent in antifouling property and lubricity, and also excellent in scratch resistance and abrasion resistance, and since the curing shrinkage of the film is small, the occurrence of warping when the article is in the form of a film is caused. Can be suppressed.

  As a method for obtaining a molded body (molded product) of the resin composition of the present invention, for example, it is injected into a mold having an arbitrary cavity shape and made of a transparent material such as quartz glass, and light (active) described later Line) A method of producing a molded body of a desired shape by curing by irradiation and removing from the mold, or if a mold is not used, a doctor blade or roll-shaped coater is placed on the moving steel belt. Examples thereof include a method for producing a sheet-like molded article by applying the resin composition of the present invention and curing the composition by actinic ray irradiation.

As a method of forming a film by the resin composition of the present invention, the film can be prepared by applying the resin composition of the present invention as a coating agent by a spin coating method or the like and curing it.
The film thickness of the formed film is preferably in the range of 0.1 to 50 μm, particularly 0.5 to 30 μm. If the film thickness is too thin, the wear resistance may decrease, and if it is too thick, the wear resistance and the like may be saturated, and the cost for imparting desired characteristics may become unnecessarily high.

As a light source for photocuring the resin composition of the present invention, usually a light source containing light having a wavelength in the range of 200 to 450 nm, such as a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a xenon lamp, a carbon arc lamp, etc. Can be used. Although the amount of irradiation is not particularly limited, it is preferably 10 to 5,000 mJ / cm ² , particularly preferably ²⁰ to 2,000 mJ / cm ² . The curing time is usually 0.5 seconds to 2 minutes, preferably 1 second to 1 minute.

  For the heat curing of the resin composition of the present invention, it is preferable to treat for 1 to 120 minutes in a temperature range of 30 to 250 ° C., particularly from the viewpoint of achieving both shortening of the curing time and prevention of deterioration of the substrate. Heat treatment is preferably performed at a temperature of ° C.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In the following, Me represents a methyl group. The weight average molecular weight of the silicone resin is a measured value in terms of polystyrene by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a developing solvent.

[Preparation Example 1]
As a starting material, the following formula (10)
In the reactor, 335.4 parts by mass (1.00 mol) of methacryloxy group-containing trimethoxysilane and 926.3 parts by mass of isopropyl alcohol were blended, and when 20% by mass tetramethylammonium hydroxide aqueous solution 15 was obtained. 2 parts by mass and 95.6 parts by mass of water (water total 6.0 mol) were added and stirred at 30 ° C. for 12 hours. Thereafter, 900 parts by mass of methyl isobutyl ketone was added, methanol and isopropyl alcohol generated by washing with water were removed, and the reaction solution was neutralized. Then, methyl isobutyl ketone was partially distilled off under reduced pressure. The obtained reaction product was a methyl isobutyl ketone solution having a volatile content of 60.0% by mass, and had a weight average molecular weight of 3,700. This reaction product undergoes hydrolysis and condensation as ideal from the results of infrared absorption light analysis and nuclear magnetic resonance analysis, and siloxane unit formula [MA1SiO _3/2 ] _1.0 [OH] _0.09 [MA1: methacryloxy derived from formula (10) It was confirmed that the photoreactive group-containing organopolysiloxane resin had a group-containing structural group (shown in the following formula (10 ′)). This is designated as resin A.

[Preparation Example 2]
As a starting material, the following formula (11)
In the reactor, 433.5 parts by mass (1.00 mol) of methacryloxy group-containing trimethoxysilane and 1270.7 parts by mass of isopropyl alcohol were blended, and when 20% by mass tetramethylammonium hydroxide aqueous solution 15 was obtained. 2 parts by mass and 95.6 parts by mass of water (water total 6.0 mol) were added and stirred at 30 ° C. for 12 hours. Thereafter, 900 parts by mass of methyl isobutyl ketone was added, methanol and isopropyl alcohol generated by washing with water were removed, and the reaction solution was neutralized. Then, methyl isobutyl ketone was partially distilled off under reduced pressure. The obtained reaction product was a methyl isobutyl ketone solution having a volatile content of 60.0% by mass, and had a weight average molecular weight of 3,900. This reaction product undergoes hydrolysis and condensation as ideal based on the results of infrared absorption light analysis and nuclear magnetic resonance analysis, and siloxane unit formula [MA2SiO _3/2 ] _1.0 [OH] _0.11 [MA2: methacryloxy derived from formula (11) It was confirmed that the photoreactive group-containing organopolysiloxane resin had a group-containing structural group (shown in the following formula (11 ′)). This is designated as resin B.

[Preparation Example 3]
As a starting material, the following formula (12)
In the reactor, 503.2 parts by mass (1.00 mol) of acryloxy group-containing trimethoxysilane and 1193.0 parts by mass of isopropyl alcohol were mixed, and when 20% by mass tetramethylammonium hydroxide aqueous solution 15 was obtained. 3 parts by mass and 95.5 parts by mass of water (total water 6.0 mol) were added and stirred at 30 ° C. for 12 hours. Thereafter, 900 parts by mass of methyl isobutyl ketone was added, methanol and isopropyl alcohol generated by washing with water were removed, and the reaction solution was neutralized. Then, methyl isobutyl ketone was partially distilled off under reduced pressure. The obtained reaction product was a methyl isobutyl ketone solution having a volatile content of 60.0% by mass and a weight average molecular weight of 13,000. This reaction product undergoes hydrolysis and condensation as ideal based on the results of infrared absorption optical analysis and nuclear magnetic resonance analysis, and siloxane unit formula [MA3SiO _3/2 ] _1.0 [OH] _0.15 [MA3: acryloxy derived from formula (12) It was confirmed that the photoreactive group-containing organopolysiloxane resin had a group-containing structural group (shown in the following formula (12 ′)). This is Resin C.

[Preparation Example 4]
As a starting material, the following formula (13)
In the reactor, 729.1 parts by mass (1.00 mol) of acryloxy group-containing trimethoxysilane and 1259.8 parts by mass of isopropyl alcohol were blended, and when 20% by mass tetramethylammonium hydroxide aqueous solution 15 was obtained. 3 parts by mass and 95.5 parts by mass of water (total water 6.0 mol) were added and stirred at 30 ° C. for 12 hours. Thereafter, 900 parts by mass of methyl isobutyl ketone was added, methanol and isopropyl alcohol generated by washing with water were removed, and the reaction solution was neutralized. Then, methyl isobutyl ketone was partially distilled off under reduced pressure. The obtained reaction product was a methyl isobutyl ketone solution having a volatile content of 60.0% by mass and a weight average molecular weight of 22,000. This reaction product undergoes hydrolysis and condensation as ideal from the results of infrared absorption light analysis and nuclear magnetic resonance analysis, and siloxane unit formula [MA4SiO _3/2 ] _1.0 [OH] _0.12 [MA4: acryloxy derived from formula (13) It was confirmed that the photoreactive group-containing organopolysiloxane resin had a group-containing structural group (shown in the following formula (13 ′)). This is designated as Resin D.

[Preparation Example 5]
As starting materials, 707.3 parts by mass (0.97 mol) of acryloxy group-containing trimethoxysilane represented by the formula (13), 19.3 parts by mass (0.03 mol) of HFPO ₃ Si (OMe) ₃ [HFPO ₃ : C ₃ F ₇ OC (CF ₃ ) FCF ₂ OC (CF ₃ ) FCH ₂ OC ₃ H ₆ —] and 1259.8 parts by mass of isopropyl alcohol were blended in the reactor, and when uniform, 20% by mass tetramethylammonium hydroxide aqueous solution. 15.3 parts by mass and 95.5 parts by mass of water (total of 6.0 mol of water) were added, and the mixture was stirred at 30 ° C. for 12 hours. Thereafter, 900 parts by mass of methyl isobutyl ketone was added, methanol and isopropyl alcohol generated by washing with water were removed, and the reaction solution was neutralized. Then, methyl isobutyl ketone was partially distilled off under reduced pressure. The obtained reaction product was a methyl isobutyl ketone solution having a volatile content of 60.0% by mass and a weight average molecular weight of 21,000. This reaction product undergoes hydrolysis and condensation as ideal based on the results of infrared absorption light analysis and nuclear magnetic resonance analysis, and the siloxane unit formula [MA4SiO _3/2 ] _0.97 [HFPO3SiO _3/2 ] _0.03 [OH] _0.12 [MA4 : Photoreactive group-containing organopolysiloxane resin having acryloxy group-containing structural group derived from formula (13), HFPO3: C ₃ F ₇ OC (CF ₃ ) FCF ₂ OC (CF ₃ ) FCH ₂ OC ₃ H ₆ —] It was confirmed that. This is designated as Resin E.

[Preparation Example 6]
As starting materials, 699.9 parts by mass (0.96 mol) of acryloxy group-containing trimethoxysilane represented by the formula (13), 19.3 parts by mass (0.03 mol) of HFPO ₃ Si (OMe) ₃ [HFPO ₃ : C ₃ F _{7 OC (CF 3) FCF 2 OC} (CF 3) FCH 2 OC 3 H 6 -], 1,19- bis (trimethoxysilyl ethyl) - pel methyl deca siloxane 0.9 part by weight (0.0009 mol), isopropyl alcohol 1259.8 parts by mass in the reactor was added, and when uniform, 15.3 parts by mass of a 20% by mass tetramethylammonium hydroxide aqueous solution and 95.5 parts by mass of water (water total 6.0 mol) were added. Stir at 30 ° C. for 12 hours. Thereafter, 900 parts by mass of methyl isobutyl ketone was added, methanol and isopropyl alcohol generated by washing with water were removed, and the reaction solution was neutralized. Then, methyl isobutyl ketone was partially distilled off under reduced pressure. The obtained reaction product was a methyl isobutyl ketone solution having a volatile content of 60.0% by mass and a weight average molecular weight of 21,000. This reaction product undergoes hydrolysis and condensation as ideal based on the results of infrared absorption optical analysis and nuclear magnetic resonance analysis, and the siloxane unit formula [R ^SE Me ₂ SiO _1/2 ] _0.0018 [Me ₂ SiO _2/2 ] _0.0072 [R ^SE SiO _3/2 ] _0.0018 [MA4SiO _3/2 ] _0.9592 [HFPO3SiO _3/2 ] _0.03 [OH] _0.06 [R ^SE : 2-silylethyl, MA4: acryloxy group-containing structural group derived from formula (13), HFPO3 : C ₃ F ₇ OC (CF ₃ ) FCF ₂ OC (CF ₃ ) FCH ₂ OC ₃ H ₆ —] was confirmed to be a photoreactive group-containing organopolysiloxane resin. This is designated as Resin F.

[Comparative Preparation Example 1]
As starting materials, 234.0 parts by mass (1.00 mol) of 3-acryloxypropyltrimethoxysilane and 539.7 parts by mass of isopropyl alcohol were blended in a reactor. When uniform, 20% by mass of tetramethylammonium hydroxide was added. A side aqueous solution (15.3 parts by mass) and water (95.5 parts by mass) (water total 6.0 mol) were added, and the mixture was stirred at 25 ° C. for 12 hours. Toluene was added, washed with water and neutralized, and then alcohol, toluene and the like were distilled off, and then methyl isobutyl ketone was added to prepare a solution.
The obtained reaction product had a volatile content of 60.0% by mass and a weight average molecular weight of 3,000. This reaction product undergoes hydrolysis and condensation as ideal from the results of infrared absorption light analysis and nuclear magnetic resonance analysis, and the siloxane unit formula [Ac3SiO _3/2 ] _1.0 [OH] _0.03 [Ac3: 3-acryloxypropyl] It was confirmed that the photoreactive group-containing organopolysiloxane resin had This is called resin G.

[Comparative Preparation Example 2]
As starting materials, 226.8 parts by mass (0.97 mol) of 3-acryloxypropyltrimethoxysilane, 19.3 parts by mass (0.03 mol) of HFPO ₃ Si (OMe) ₃ [HFPO ₃ : C ₃ F ₇ OC (CF ₃ ) FCF ₂ OC (CF ₃ ) FCH ₂ OC ₃ H ₆ —] and 608.5 parts by mass of isopropyl alcohol were blended in the reactor, and when uniform, 15.3 parts by mass of a 20% by mass tetramethylammonium hydroxide aqueous solution was obtained. , 95.5 parts by mass of water (total 6.0 mol of water) was added and stirred at 25 ° C. for 12 hours. Toluene was added, washed with water and neutralized, and then alcohol, toluene and the like were distilled off, and then methyl isobutyl ketone was added to prepare a solution.
The obtained reaction product had a volatile content of 60.0% by mass and a weight average molecular weight of 2,200. This reaction product undergoes hydrolytic condensation as ideal based on the results of infrared absorption light analysis and nuclear magnetic resonance analysis, and the siloxane unit formula [Ac3SiO _3/2 ] _0.97 [HFPO3SiO _3/2 ] _0.03 [OH] _0.04 [Ac3 : _{3-acryloxypropyl, HFPO3: C 3 F 7 OC} (CF 3) FCF 2 OC (CF 3) FCH 2 OC 3 H 6 - was confirmed to be] photoreactive group-containing organopolysiloxane resin having a . This is Resin H.

[Comparative Preparation Example 3]
As starting materials, 3-acryloxypropyltrimethoxysilane 224.6 parts by mass (0.96 mol), HFPO ₃ Si (OMe) ₃ 19.3 parts by mass (0.03 mol) [HFPO ₃ : C ₃ F ₇ OC (CF ₃ ) FCF ₂ OC (CF ₃ ) FCH ₂ OC ₃ H ₆ —], 1,19-bis (trimethoxysilylethyl) -permethyldecasiloxane 0.9 parts by mass (0.0009 mol), isopropyl alcohol 612.7 parts by mass Was mixed in the reactor, and when uniform, 15.3 parts by mass of a 20% by mass tetramethylammonium hydroxide aqueous solution and 95.5 parts by mass of water (total of 6.0 mol of water) were added, and the mixture was added at 25 ° C. for 12 hours. Stir. Toluene was added, washed with water and neutralized, and then alcohol, toluene and the like were distilled off, and then methyl isobutyl ketone was added to prepare a solution.
The obtained reaction product had a volatile content of 60.0% by mass and a weight average molecular weight of 3,000. This reaction product undergoes hydrolysis and condensation as ideal based on the results of infrared absorption optical analysis and nuclear magnetic resonance analysis, and the siloxane unit formula [R ^SE Me ₂ SiO _1/2 ] _0.0018 [Me ₂ SiO _2/2 ] _0.0072 [R ^SE SiO _3/2 ] _0.0018 [Ac3SiO _3/2 ] _0.9592 [HFPO3SiO _3/2 ] _0.03 [OH] _0.043 [R ^SE : 2-silylethyl, Ac3: acryloxypropyl, HFPO3: C ₃ F ₇ OC (CF ₃ ) It was confirmed that the photoreactive group-containing organopolysiloxane resin had FCF ₂ OC (CF ₃ ) FCH ₂ OC ₃ H ₆ —]. This is Resin I.

[Example 1]
Organopolysiloxane resin (resin A) obtained in Preparation Example 1: 25 parts by mass (converted to main component), trimethylolpropane triacrylate: 10 parts by mass, dicyclopentadienyl diacrylate (Kyoeisha Chemical Co., Ltd. light acrylate) DCP-A): 60 parts by mass, urethane acrylate oligomer (UF-8001 manufactured by Kyoeisha Chemical Co., Ltd.): 5 parts by mass were mixed, and methyl isobutyl ketone was distilled off under reduced pressure. Thereafter, Darocur 1173 (trade name, manufactured by Ciba Specialty Chemicals): 2.5 parts by mass as a photopolymerization initiator was mixed to obtain a transparent resin composition.
Next, the film was cast to a thickness of 0.2 mm using a roll coater, and irradiated with light with an 80 W high-pressure mercury lamp for 2 seconds (integrated irradiation amount: 200 mJ / cm ² ) to cure to a predetermined thickness. A molded body was obtained.

[Examples 2 to 4 and Comparative Example 1]
In Example 1, resin B, C, D, and G were used in place of the resin A, and a resin molded body was obtained in the same manner as in Example 1 except that. These formulation details are shown in Table 1.

About the obtained molded object, various characteristics were measured with the following method.
[Molded product characteristics]
(1) Glass transition temperature Dynamic thermomechanical analysis, heating rate 5 ° C / min, chuck distance 10mm
(2) Linear expansion coefficient (JIS K 7197)
Thermomechanical analysis, heating rate 5 ° C / min, compression load 0.1N
(3) Total light transmittance (JIS K 7361-1)
Spectroscopic ellipsometry, sample thickness 0.2mm
(4) Birefringence Spectroscopic ellipsometry, sample thickness 0.2mm
Table 2 shows the physical property values of the obtained molded body.

[Example 5]
Organopolysiloxane resin (resin A) obtained in Preparation Example 1: 60 parts by mass (converted to main component), hexanediol diacrylate: 40 parts by mass, Darocur 1173 (trade name, manufactured by Ciba Specialty Chemicals) as a photopolymerization initiator : 5 parts by mass were mixed to obtain a transparent resin composition.
Next, it was applied to a polycarbonate plate to a thickness of 5 μm using a bar coater (No. 5), dried with a dryer at 50 ° C. for 10 minutes, and then irradiated with light with an 80 W high pressure mercury lamp for 2 seconds ( (A cumulative irradiation amount of 200 mJ / cm ² ) was cured to form a film.

[Examples 6 to 10 and Comparative Examples 2 to 4]
In Example 5, instead of the resin A, resins B to I were used, and other than that was obtained in the same manner as in Example 5 to obtain a cured film. These formulation details are shown in Table 3.

Various characteristics of the cured film on the obtained polycarbonate plate and a PET film on which a separately cured film was formed were measured as follows.
[Hardened film properties]
(1) Magic ink resistance A line was drawn with a commercially available oil-based magic ink on the cured film, and the wiping property when wiped with a waste cloth was visually observed and evaluated according to the following evaluation criteria. ○: Magic ink remains not observed after wiping with waste (wiping property), ×: Magic ink remaining is observed after wiping with waste (no wiping property).
(2) Antifouling property The water contact angle and the trioleic acid contact angle were measured using a contact angle meter (CA-X150 type, manufactured by Kyowa Interface Science) (the larger the contact angle, the better the antifouling property).
(3) Scratch resistance, abrasion resistance In accordance with ASTM D 1044, a cured film is subjected to a wear test (500 g load 100 rotations) using a Taber abrasion tester (with wear wheel CS-10F). The turbidity of the cured film was measured using a turbidimeter (NHD2000, manufactured by Nippon Denshoku Industries Co., Ltd.), and the value of [turbidity after abrasion test-turbidity before abrasion test] was defined as ΔHaze (haze) (ΔHaze) If the ratio is 15 or less, the scratch resistance and wear resistance are good.) The thickness of these samples is 5 μm.
(4) Curing shrinkage About the degree of warpage (curl) of the entire film due to shrinkage, a film obtained by forming a cured film with a thickness of 5 μm on a flat 10 cm × 10 cm PET film and fixing it to the horizontal plane at the film center point Evaluation was made based on the distance from the horizontal surface of the edge (the edge closest to the film center). In this case, it means that shrinkage is so large that a numerical value is large.
Table 4 shows the physical property values of the obtained cured film.

  As described above, the resin composition of the present invention includes a predetermined component silicone resin having a siloxane unit having a (meth) acryloxy group as a main constituent unit, and the hardness and toughness of the cured product are balanced in a high dimension. Since both are achieved, it is a suitable result as a functional film material and an antifouling and scratch-resistant coating material.

Claims (10)

The following siloxane unit formula (1)
[Wherein, X is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ^{1 to} R ⁶ are substituted or unsubstituted monovalent hydrocarbon groups having 1 to 10 carbon atoms, and the substituent is fluorine. Atom, chlorine atom, bromine atom, (meth) acryloxy group, epoxy structure-containing group, mercapto group, isocyanate group, amino functional group, perfluoroalkyl group, poly (hexafluoropropylene oxide) structure-containing group, silyl group Or one or more monovalent organic groups. However, any one of R ^{1 to} R ^{6 is represented by} the following formula (2)
(Wherein R ⁷ is the following formula (3)
A is a branched or unbranched carbon group having 2 to 10 carbon atoms and may have an oxygen atom between them, and does not contain any other hetero atom (n + 1) -valent hydrocarbon group R ⁸ is independently a hydrogen atom or a methyl group, m is an integer of 1 to 10, and n is an integer of 1 to 5. The CH ₂ ═CR ⁸ —COO— group may be bonded to any one or more of the carbon atoms of A. )
The number of siloxane units substituted by the organic group represented by the formula (2) with respect to the total siloxane units is 20 to 100 mol%, and a is an average of 0 ≦ a < 0.4, b is average 0 ≦ b <0.5, c is average 0 <c ≦ 1, d is average 0 ≦ d <0.4, and e is average 0 ≦ e <0.4. 0.2 and a + b + c + d = 1. ]
The light and thermosetting resin composition containing the silicone resin represented by these.   The light and thermosetting resin composition according to claim 1, wherein m in the formula (2) is 3. The organic group represented by the formula (2) is represented by the following formulas (4) to (8).
(Wherein R ⁸ has the same meaning as described above.)
The light and thermosetting resin composition according to claim 2, which is any one of the structural groups represented by the above, or a combination of two or more thereof.   The light and thermosetting resin composition according to any one of claims 1 to 3, wherein the silicone resin has a weight average molecular weight of 2,000 to 50,000.   5. The siloxane unit in which the silicone resin is substituted with a perfluoroalkyl group or a poly (hexafluoropropylene oxide) structure-containing group with respect to the total siloxane units is 0.1 to 20 mol%. The light and thermosetting resin composition according to Item.   Furthermore, the light and thermosetting resin composition of any one of Claims 1-5 containing a polyfunctional (meth) acryl compound.   Furthermore, the light and thermosetting resin composition of any one of Claims 1-6 containing 1 or more types of metal oxide microparticles | fine-particles.   The light and thermosetting resin composition according to any one of claims 1 to 7, further comprising at least one of a radical photopolymerization catalyst and a thermal condensation catalyst.   A molded article obtained by curing the light and thermosetting resin composition according to claim 1.   An article formed by forming a cured film of the light and thermosetting resin composition according to any one of claims 1 to 8.