JP2015205956A - Composition, film formed by curing the composition and resin-made member having the film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin member exhibiting a high level of weather resistance, a film constituting the resin member, and a composition for obtaining the film. SOLUTION: The total of 100 parts by mass of the following component (A), component (B) and component (C) is 20 to 80 parts by mass of component (A), and 5 to 50 parts by mass of component (B). The composition characterized by including 1-35 mass parts of said (C) component. Component (A): Isocyanuric ring-containing urethane (meth) acrylate compound (B) Component: Di (meth) acrylate compound (C) Component: Non-volatile component of the reaction product of silane compound and colloidal silica [Selection] None

Description

  The present invention relates to a composition containing a specific component, a film obtained by curing the composition, and a resin member having the film.

  Resin members such as polycarbonate are lighter in specific gravity and lighter than inorganic glass, are easy to process, and are resistant to impact, and are used as materials for a wide variety of applications including those for vehicles. On the other hand, resin members have drawbacks such that the surface is easily scratched and gloss and transparency are easily lost, they are easily attacked by organic solvents, weather resistance (for example, light stability against ultraviolet rays, etc.) and heat resistance are poor. . Automobile window glass and the like are often exposed to sunlight for a long period of time. Therefore, when using a resin member for automobiles, it is necessary to make the resin member imparted with wear resistance and weather resistance by means such as covering the surface of the resin member body with a protective film.

  Patent Document 1 discloses a first layer obtained by curing a primer composition having excellent weather resistance on the surface of a resin member body, and a coating composition having excellent wear resistance on the first layer. A plastic article provided with a cured second layer is disclosed. The plastic article described in Patent Document 1 has both wear resistance and weather resistance at a high level. However, when not only the coating composition but also the primer composition as in Patent Document 1, the number of steps increases, which is not desirable from the viewpoint of productivity. Therefore, a coating agent that can form a protective film exhibiting sufficient abrasion resistance and weather resistance without using an undercoat composition has been eagerly desired.

  Therefore, the present inventors newly provide a coating agent satisfying such conditions and containing a specific component in a specific blending amount, and a protective film obtained by curing the coating agent exhibits wear resistance and weather resistance. (Patent Document 2).

JP 2001-214122 A Japanese Patent No. 5146790

Now, a high level of weather resistance is required especially for resin members used outdoors.
The present invention has been made in view of such circumstances, and provides a resin member exhibiting a higher level of weather resistance, a film constituting the resin member, and a composition for obtaining the film. With the goal.

  This inventor earnestly examined about the relationship between the structural component of a composition, and the weather resistance of resin-made members. As a result of many trials and errors, the inventor has found that a composition, a film, and a resin member that can solve the above-described problems can be obtained by including a specific compound in the composition.

  That is, the composition of the present invention comprises 20 to 80 parts by mass of the component (A) and 100 parts by mass of the component (B) with respect to a total of 100 parts by mass of the following components (A), (B) and (C). 5 to 50 parts by mass and 1 to 35 parts by mass of the component (C).

(A) component:
Isocyanuric ring-containing urethane (meth) acrylate compound represented by the following general formula (1)

（一般式（１）において、Ｒ^１、Ｒ^２およびＲ^３はそれぞれ独立して炭素数２〜１０の２価の有機基を表し、Ｒ^４、Ｒ^５およびＲ^６はそれぞれ独立して水素またはメチル基を表す。）

(In General Formula (1), R ¹ , R ² and R ³ each independently represents a divalent organic group having 2 to 10 carbon atoms, and R ⁴ , R ⁵ and R ⁶ are each independently hydrogen or Represents a methyl group.)

(B) component:
Di represented by the following general formula (2) (meth) acrylate compound ^{_{CH 2 = CR 21 CO- (OR}} 23) m -A 1 - (R 24 O) n -COCR 22 = CH 2 ... (2)
(In the general formula (2), R ²¹ and R ²² each independently represent hydrogen or a methyl group, R ²³ and R ²⁴ each independently represent a divalent hydrocarbon group having 2 to 10 carbon atoms, m and n each independently represents an integer of 0 or more, and A ¹ is represented by the following general formula (2-1).

（一般式（２−１）において、Ｒ^２５およびＲ^２６はそれぞれ独立して水素、炭素数１〜６のアルキル基またはフェニル基を表す。Ｂ^１は、ＣＲ^２７Ｒ^２８、ＳＯ_２、Ｃ＝ＣＸ_２、下記一般式（２−２）を表す。Ｒ^２７およびＲ^２８はそれぞれ独立して水素、炭素数１〜６のアルキル基、炭素数１〜６のＸ置換アルキル基、フェニル基を表す。Ｘはハロゲンを意味する。または、Ｒ^２７およびＲ^２８は互いに結合している炭素とともにアルキル置換され得る飽和炭化水素環を形成する。）

(In General Formula (2-1), R ²⁵ and R ²⁶ each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, or a phenyl group. B ¹ represents CR ²⁷ R ²⁸ , SO ₂ , C = CX ₂ represents the following general formula (2-2): R ²⁷ and R ²⁸ each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, an X-substituted alkyl group having 1 to 6 carbon atoms, or a phenyl group. X represents halogen, or R ²⁷ and R ²⁸ together with the carbons attached to each other form a saturated hydrocarbon ring that can be alkyl substituted.)

（一般式（２−２）において、Ｒ^２９、Ｒ^３０、Ｒ^３１およびＲ^３２はそれぞれ独立して水素または炭素数１〜６のアルキル基を表す。）

(In general formula (2-2), R ²⁹ , R ³⁰ , R ³¹ and R ³² each independently represent hydrogen or an alkyl group having 1 to 6 carbon atoms.)

Component (C):
A reaction product obtained by reacting a silane compound (c1) represented by the following general formula (3) with colloidal silica (c2) at a mass ratio of (c1) and (c2) of 9: 1 to 1: 9. Nonvolatile components, including those obtained by chemically modifying (c2) with (c1).

（一般式（３）において、Ｒ^１３は水素または１価の有機基を表し、Ｒ^１４は炭素数１〜６の２価の炭化水素を表し、ｚは０．１以上３以下の正の数を表す。また、ｚが３未満の場合に（ｃ１）は縮合物を含み、該縮合物の１分子中のＲ^１３は２種以上の異なる基を含んでいてもよい。）

(In General Formula (3), R ¹³ represents hydrogen or a monovalent organic group, R ¹⁴ represents a divalent hydrocarbon having 1 to 6 carbon atoms, and z is a positive number of 0.1 or more and 3 or less. In addition, when z is less than 3, (c1) contains a condensate, and R ^{13 in} one molecule of the condensate may contain two or more different groups.

  The film of the present invention is obtained by curing the above composition.

The resin member of the present invention comprises a resin member main body having a repeating unit represented by the following general formula (4), and the film covering the resin member main body.
^{- (A 2 -CO) - ...} (4)
(In the general formula (4), ^{A 2} is represented by the following general formula (4-1).)

（一般式（４−１）において、Ｒ^４１およびＲ^４２はそれぞれ独立して水素、炭素数１〜６のアルキル基またはフェニル基を表す。Ｂ^２は、ＣＲ^４３Ｒ^４４、ＳＯ_２、Ｃ＝ＣＸ_２、下記一般式（４−２）を表す。Ｒ^４３およびＲ^４４はそれぞれ独立して水素、炭素数１〜６のアルキル基、炭素数１〜６のＸ置換アルキル基、フェニル基を表す。Ｘはハロゲンを意味する。または、Ｒ^４３およびＲ^４４は互いに結合している炭素とともにアルキル置換され得る飽和炭化水素環を形成する。）

(In General Formula (4-1), R ⁴¹ and R ⁴² each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, or a phenyl group. B ² represents CR ⁴³ R ⁴⁴ , SO ₂ , C = CX ₂ represents the following general formula (4-2): R ⁴³ and R ⁴⁴ each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, an X-substituted alkyl group having 1 to 6 carbon atoms, or a phenyl group. X represents halogen, or R ⁴³ and R ⁴⁴ together with the carbons attached to each other form a saturated hydrocarbon ring that can be alkyl substituted.)

（一般式（４−２）において、Ｒ^４５、Ｒ^４６、Ｒ^４７およびＲ^４８はそれぞれ独立して水素または炭素数１〜６のアルキル基を表す。）

(In the general formula (4-2), R ⁴⁵ , R ⁴⁶ , R ⁴⁷ and R ⁴⁸ each independently represent hydrogen or an alkyl group having 1 to 6 carbon atoms.)

  The resin member of the present invention exhibits a high level of weather resistance.

It is a perspective view showing typically a sunroof using a member for vehicles which is one mode of a resin member of the present invention. It is sectional drawing which shows typically the window glass of the member for vehicles which is one aspect | mode of the resin-made members of this invention. It is a table | surface which shows the result of an Example among the evaluation examples 1. FIG. It is a table | surface which shows the result of a comparative example among the evaluation examples 1. FIG.

  The best mode for carrying out the present invention will be described below. Unless otherwise specified, the numerical range “x to y” described in this specification includes the lower limit x and the upper limit y. The numerical range can be configured by arbitrarily combining these upper limit value and lower limit value and the numerical values listed in the examples. Furthermore, numerical values arbitrarily selected from the numerical value range can be used as upper and lower numerical values. In the present specification, an acryloyl group or a methacryloyl group is represented as a (meth) acryloyl group, and an acrylate or methacrylate is represented as a (meth) acrylate.

The composition of the present invention (hereinafter sometimes simply referred to as “composition”) is obtained by adding the component (A) to 100 parts by mass of the total of the component (A), the component (B) and the component (C). 20 to 80 parts by mass, 5 to 50 parts by mass of the component (B), and 1 to 35 parts by mass of the component (C). When the composition of the present invention is applied to the surface of a resin member body and cured to form a film, the adhesion between the film and the resin member body is improved. The composition of the present invention can be grasped for application, coating, and film formation.
First, the component (A) will be described. The component (A) is an isocyanuric ring-containing urethane (meth) acrylate compound represented by the following general formula (1).

In the general formula (1), R ¹ , R ² and R ³ each independently represent a divalent organic group having 2 to 10 carbon atoms. The divalent organic group having 2 to 10 carbon atoms is preferably an alkylene group having 2 to 4 carbon atoms such as ethylene group, trimethylene group, propylene group and tetramethylene group. In addition, the compound represented by the general formula (1) includes an ε-caprolactone-modified compound. In this case, the divalent organic group having 2 to 10 carbon atoms includes —COCH ₂ CH ₂ CH ₂ CH ₂ CH _2. O- or _{-OCOCH 2 CH 2 CH 2 CH 2} CH 2 - containing. Those in which R ¹ , R ² and R ³ are all tetramethylene groups are particularly preferred because a film having particularly excellent wear resistance and weather resistance can be obtained.

In the general formula (1), R ⁴ , R ⁵ and R ⁶ each independently represent hydrogen or a methyl group. Here, the compound in which R ⁴ , R ⁵ and R ⁶ are all hydrogen is particularly preferable in terms of excellent curability.

  The component (A) is synthesized by an addition reaction between a nurate type trimer of hexamethylene diisocyanate and a hydroxyalkyl (meth) acrylate or a caprolactone modified product thereof. Although this addition reaction can be performed without a catalyst, a catalyst such as a tin-based catalyst such as dibutyltin dilaurate or an amine-based catalyst such as triethylamine is preferably used in order to promote the reaction efficiently.

  The content ratio of the component (A) in the composition of the present invention is 20 to 80 parts by mass with respect to a total of 100 parts by mass of the component (A), the component (B), and the component (C), preferably 35 to 35 parts by mass. It is 75 mass parts, More preferably, it is 50-70 mass parts, More preferably, it is 55-65 mass parts. (A) By making the content rate of a component into 20-80 mass parts, the film | membrane excellent in abrasion resistance and a weather resistance is obtained.

Next, the component (B) will be described. The component (B) is a di (meth) acrylate compound represented by the following general formula (2).
^{_{CH 2 = CR 21 CO- (OR}} 23) m -A 1 - (R 24 O) n -COCR 22 = CH 2 ... (2)

In the general formula (2), R ²¹ and R ²² each independently represent hydrogen or a methyl group. R ²³ and R ²⁴ each independently represent a divalent hydrocarbon group having 2 to 10 carbon atoms. The divalent hydrocarbon group having 2 to 10 carbon atoms is preferably an alkylene group having 2 to 4 carbon atoms such as ethylene group, trimethylene group, propylene group and tetramethylene group. m and n each independently represents a number of 0 or more. m + n is preferably in the range of 1 to 100, more preferably in the range of 2 to 70, still more preferably in the range of 3 to 50, and particularly preferably in the range of 10 to 30. Note that m and n represent the average number of moles of (OR ²³ ) and (R ²⁴ O) per mole of the di (meth) acrylate compound represented by the general formula (2).
A ¹ is represented by the following general formula (2-1).

In General Formula (2-1), R ²⁵ and R ²⁶ each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, or a phenyl group. Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, an n-propyl group, and an i-propyl group. R ²⁵ and R ²⁶ are preferably substituted at the 2-position of the benzene ring as viewed from the substitution position of O on the benzene ring.

In General Formula (2-1), B ¹ represents CR ²⁷ R ²⁸ , SO ₂ , C═CX ₂ , and the following General Formula (2-2).

R ²⁷ and R ²⁸ each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, an X-substituted alkyl group having 1 to 6 carbon atoms, or a phenyl group. Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, and an n-propyl group. X means halogen such as chlorine.

R ²⁷ and R ²⁸ can form a saturated hydrocarbon ring that can be alkyl-substituted together with carbons bonded to each other. Examples of saturated hydrocarbon rings that can be substituted with alkyl include cyclopentane ring, cyclohexane ring, cycloheptane ring, 3,3-dimethylcyclohexane ring, 3,5-dimethylcyclohexane ring, and 3,3,5-trimethylcyclohexane ring. .
Examples of C = CX ₂ include C = CCl ₂ and C = CBr ₂ .
General formula (2-2) is as follows.

In General Formula (2-2), R ²⁹ , R ³⁰ , R ³¹ and R ³² each independently represent hydrogen or an alkyl group having 1 to 6 carbon atoms. Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, and an n-propyl group. The substitution positions of R ²⁹ R ³⁰ C and CR ³¹ R ³² with respect to the benzene ring are preferably meta or para positions.

Listed chemical structure of a particular A ¹ below.

The component (B) includes CH ₂ ═CR ²¹ —CO or CO—CR ²² ═CH ₂ derivative corresponding to the (meth) acrylate moiety, and (OR ²³ ) _m or (R ²⁴ O) _n corresponding to the alkylene glycol moiety. and derivatives, the a ¹ derivatives can be prepared by causing an appropriate reaction. Moreover, in order to obtain (B) component, you may purchase the compound applicable to the (B) component marketed.

  The content rate of (B) component in the composition of this invention is 5-50 mass parts with respect to a total of 100 mass parts of (A) component, (B) component, and (C) component, Preferably it is 10-45. It is 20 mass parts, More preferably, it is 20-40 mass parts, More preferably, it is 22-38 mass parts, Most preferably, it is 25-35 mass parts. (B) By making the content rate of a component into 5-50 mass parts, the film | membrane excellent in adhesiveness is obtained. When the content ratio of the component (B) is less than 5 parts by mass, the adhesion of the film may be lowered. When the content rate of (B) component exceeds 50 mass parts, the hardness of a film | membrane may fall.

  Next, the component (C) will be described. (C) component reacts silane compound (c1) represented by the following general formula (3) and colloidal silica (c2) at a mass ratio of (c1) and (c2) from 9: 1 to 1: 9. A non-volatile component of the reaction product obtained by chemical modification of (c1) with (c1).

  In addition, although the synthesis | combination of (C) component is normally performed in a solvent, (C) component means the component except the water and organic solvent which were used by reaction. Further, the component (C) is a component excluding alcohol generated by hydrolysis of alkoxysilane and water generated by condensation of silanol. That is, the component (C) means a non-volatile component in the reaction product.

In the general formula (3), R ¹³ represents hydrogen or a monovalent organic group. Specific examples of the monovalent organic group for R ¹³ include an alkyl group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms having alkoxy having 1 to 6 carbon atoms, and other C, H, and O C1-C6 organic group which consists of an atom is mentioned.

In terms of reactivity, R ¹³ is preferably hydrogen or a monovalent organic group that may have an oxygen atom having 1 to 6 carbon atoms, and more preferably hydrogen or an alkyl group having 1 to 6 carbon atoms.

In the general formula ^{(3), R 14} represents a divalent saturated hydrocarbon group having 1 to 6 carbon atoms. R14 may be linear or branched. Examples of the linear saturated hydrocarbon group include ethylene group, 1,3-propylene group (trimethylene group), 1,4-butylene group (tetramethylene group), 1,5-pentanediyl group (pentamethylene group), 1, A 6-hexanediyl group (hexamethylene group) can be exemplified. Examples of the branched alkylene group include 1,2-propylene group, 1,2-butylene group, 1,3-butylene group, 2,3-butylene group, 1,3-pentanediyl group, 2,4-pentanediyl group, 2 , 5-hexanediyl group, 2-methyl-1,3-propylene group, 2-ethyl-1,3-propylene group, and 3-methyl-1,5-pentanediyl group.

R ¹⁴ is particularly preferably a linear divalent saturated hydrocarbon group having 3 to 6 carbon atoms. R ¹⁴ is preferably a divalent saturated hydrocarbon group having 1 to 6 carbon atoms, and more preferably a linear chain having 3 to 6 carbon atoms, in that the film has excellent wear resistance and weather resistance. A divalent saturated hydrocarbon group is more preferred.

In the general formula (3), z satisfies 0.1 ≦ z ≦ 3. z represents the average number of moles of remaining alkoxy groups per mole of Si atoms. (C1) indicates an alkoxysilane monomer when z is 3, and indicates an alkoxysilane condensate or a mixture of an alkoxysilane condensate and an alkoxysilane monomer when z is less than 3. In addition, the value of z can be calculated | required from the ¹ H-NMR spectrum of (c1), and the integral ratio of hydrogen.

  By setting z to 0.1 or more, colloidal silica is effectively surface-modified, and the film has excellent scratch resistance. From the viewpoint of reactivity, z preferably satisfies 0.4 ≦ z ≦ 3, and more preferably satisfies 0.8 ≦ z ≦ 3.

When (c1) is a condensate, R ¹³ may have two or more different chemical structures.

  In addition, the 3,4,5,6-tetrahydrophthalimide group of the general formula (3) may be dimerized when the 3,4,5,6-tetrahydrophthalimide group reacts with each other when absorbing ultraviolet rays.

  For the preferred method for producing the compound of the general formula (3), see the description in Patent Document 2 above.

  (C2) is colloidal silica, and various types can be used, but those in which spherical particles are uniformly dispersed are preferable, for example, those in which alcohol particles are uniformly dispersed are more preferable.

The average primary particle size of (c2) is preferably 1 to 100 nm, more preferably 5 to 60 nm, and particularly preferably 5 to 30 nm. By setting the average primary particle size of (c2) to 1 nm or more, the wear resistance can be improved, and by setting it to 100 nm or less, the dispersion stability of the colloidal solution can be improved. In the present invention, the average primary particle diameter means a value calculated from the specific surface area by the BET method. Moreover, the specific surface area of (c2) is in the range of 30 to 3,000 m ² / g.

  The method for synthesizing the component (C) is preferably a method in which (c1) and (c2) are charged at a predetermined mass ratio in the presence of an organic solvent containing water and then heated to react. The heating temperature and time are different depending on the presence or absence of a catalyst and the like, and thus cannot be defined unconditionally, but are preferably 40 to 140 ° C., preferably 60 to 120 ° C. and 0.5 to 20 hours.

  Component (C) includes not only silica fine particles whose surface is modified in (c1), but also hydrolyzed condensates of (c1) that do not contain silica fine particles and by-products when producing (c1). The component (C) is defined including them.

  The charge mass ratio of (c1) and (c2) when synthesizing the component (C) is 1: 9 to 9: 1, more preferably 2: 8 to 7: 3, still more preferably 2: 8 to 6: 4. By setting the mass ratio of (c1) and (c2) to 1: 9 to 9: 1, it is possible to achieve both wear resistance and weather resistance of the film.

  The amount of water charged into the reaction system when the component (C) is synthesized is preferably 0.3 to 10 mol, and more preferably 0.5 to 5 mol, relative to 1 mol of the alkoxy group. By setting the amount of water charged to 0.3 to 10 mol with respect to 1 mol of the alkoxy group, the surface of the silica fine particles can be efficiently modified without causing the silica fine particles to gel.

  (C) As an organic solvent at the time of synthesize | combining a component, what melt | dissolves water uniformly is preferable, More preferably, it is an alcohol solvent with a boiling point of 100 to 200 degreeC, More preferably, it is a boiling point of 100 degreeC which has an ether bond It is an alcohol solvent at ˜200 ° C. Specific examples of preferred organic solvents include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether and ethylene glycol. And monobutyl ether.

  In addition, although (C) component can be manufactured without a catalyst, you may add an acid catalyst and an alkali catalyst.

  After the reaction of (c1) and (c2) is completed, water contained in the liquid after the reaction may be removed. The liquid after the reaction may be heated and / or decompressed to distill off water and the organic solvent. At this time, it is preferable to add an organic solvent having a boiling point higher than that of water to the solution after the reaction.

  The content rate of (C) component in the composition of this invention is 1-35 mass parts with respect to a total of 100 mass parts of (A) component, (B) component, and (C) component, Preferably it is 1-35 mass parts. 30 mass parts, More preferably, it is 3-25 mass parts, More preferably, it is 5-20 mass parts, Most preferably, it is 5-15 mass parts. (C) By making the content rate of a component into 1-35 mass parts, the film | membrane excellent in abrasion resistance and a weather resistance is obtained. When the proportion of the component (C) is 1 part by mass or more, the wear resistance of the film is improved. However, when the component (C) is excessive, the film tends to shrink or the organic portion of the film is rapidly decomposed, so that the weather resistance of the film is lowered.

  In the composition of the present invention, additives such as a radical polymerization initiator, an ultraviolet absorber, an organic solvent, a hindered amine light stabilizer, a surface modifier, a polymerization inhibitor, an antioxidant, an unsaturated compound, and an organic polymer are added. You may mix.

  By using a radical polymerization initiator, the composition of the present invention can be rapidly cured. As the radical polymerization initiator, a known photo radical polymerization initiator and thermal radical polymerization initiator may be employed. A radical polymerization initiator may be used independently and may use 2 or more types together. The preferable content rate of the radical polymerization initiator in the composition of this invention is 0.1-10 mass parts with respect to a total of 100 mass parts of (A) component, (B) component, and (C) component, and more. Preferably it is 0.5-5 mass parts, Most preferably, it is 1-3 mass parts.

  Specific examples of the photo radical polymerization initiator include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propane. -1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-1- [4- (methylthio) phenyl] 2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, diethoxyacetophenone, oligo {2-hydroxy-2-methyl- 1- [4- (1-methylvinyl) phenyl] propanone} and 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropioni) ) Benzyl] phenyl} -2-methyl-propan-1-one and the like acetophenone compounds; benzophenone, 4-phenylbenzophenone, 2,4,6-trimethylbenzophenone, 4-benzoyl-4′-methyl-diphenylsulfide, etc. Benzophenone compounds such as methylbenzoylformate, α-ketoesters such as 2- (2-oxo-2-phenylacetoxyethoxy) ethyl ester of oxyphenylacetic acid and 2- (2-hydroxyethoxy) ethyl ester of oxyphenylacetic acid Compound; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpenty Phosphine oxide compounds such as ruphosphine oxide; benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether; titanocene compounds; 1- [4- (4-benzoylphenylsulfanyl) Acetophenone / benzophenone hybrid photoinitiators such as phenyl] -2-methyl-2- (4-methylphenylsulfinyl) propan-1-one; 2- (O-benzoyloxime) -1- [4- (phenylthio)] Examples include oxime ester photopolymerization initiators such as -1,2-octanedione; and camphorquinone.

  Examples of the thermal radical polymerization initiator include organic peroxides and azo compounds.

  Specific examples of the organic peroxide include 1,1-bis (t-butylperoxy) 2-methylcyclohexane, 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane, , 1-bis (t-hexylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, , 2-bis (4,4-di-butylperoxycyclohexyl) propane, 1,1-bis (t-butylperoxy) cyclododecane, t-hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl- , 5-di (m-toluoylperoxy) hexane, t-butylperoxyisopropyl monocarbonate, t-butylperoxy 2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, 2,5-dimethyl-2,5 -Di (benzoylperoxy) hexane, t-butylperoxyacetate, 2,2-bis (t-butylperoxy) butane, t-butylperoxybenzoate, n-butyl-4,4-bis (t-butyl) Peroxy) valerate, di-t-butylperoxyisophthalate, α, α′-bis (t-butylperoxy) diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-di (t- Butylperoxy) hexane, t-butylcumyl peroxide, di-t-butylperoxide , P-menthane hydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, diisopropylbenzene hydroperoxide, t-butyltrimethylsilyl peroxide, 1,1,3,3 -Tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-hexyl hydroperoxide and t-butyl hydroperoxide can be exemplified.

  Specific examples of the azo compound include 1,1′-azobis (cyclohexane-1-carbonitrile), 2- (carbamoylazo) isobutyronitrile, 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile. And azodi-t-octane and azodi-t-butane.

  By using the ultraviolet absorber, it is possible to suppress deterioration due to ultraviolet rays of the resin member main body covered with the film of the present invention. As the ultraviolet absorber, a known one may be adopted. An ultraviolet absorber may be used independently and may use 2 or more types together. The content of the ultraviolet absorber in the composition of the present invention is preferably 1 to 12 parts by mass, and preferably 2 to 10 parts by mass with respect to a total of 100 parts by mass of the component (A), the component (B), and the component (C). Part is more preferable, and 3 to 7 parts by mass is further preferable.

  By setting the content ratio of the ultraviolet absorber to 1 to 12 parts by mass, the abrasion resistance and weather resistance of the film can be suitably achieved. If the ultraviolet absorber is less than 1 part by mass, a resin member exhibiting sufficient weather resistance may not be obtained. On the other hand, when there are too many ultraviolet absorbers, not only the abrasion resistance of a film | membrane will fall, but it exists in the tendency for the weather resistance of resin-made members also to fall.

  Specific examples of the ultraviolet absorber include 2- [4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl)- 1,3,5-triazine, 2- [4-[(2-hydroxy-3-tridecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1, 3,5-triazine, 2- [4-[(2-hydroxy-3- (2-ethylhexyloxy) propyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-4-butyroxyphenyl) -6- (2,4-bis-butyroxyphenyl) -1,3,5-triazine, 2- (2-hydroxy-4 Triazine ultraviolet absorbers such as [1-octyloxycarbonylethoxy] phenyl) -4,6-bis (4-phenylphenyl) -1,3,5-triazine; 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, 2- (2-hydroxy-5-tert-butylphenyl) -2H-benzotriazole, 2- [2-hydroxy-5- (2- (Meth) acryloyloxyethyl) phenyl] -2H-benzotriazole and other benzotriazole UV absorbers; 2,4-dihydroxybenzophenone and 2-hydroxy-4-methoxybenzophenone and other benzophenone UV absorbers, ethyl-2- Cyano-3,3-diphenyl acrylate, octyl-2-cyano-3,3-diphenyl Cyanoacrylate ultraviolet absorbers such as acrylate, titanium oxide fine particles, zinc oxide fine particles, inorganic fine particles that absorb ultraviolet radiation, such as tin oxide fine particles can be exemplified. A benzotriazole-based ultraviolet absorber having a (meth) acryloyl group is particularly preferred in that the weather resistance and wear resistance of the film can be suitably achieved.

  By using the organic solvent, the composition of the present invention can be uniformly applied to the resin member body. An organic solvent may be used independently and may use 2 or more types together.

  Specific examples of the organic solvent include alcohols such as ethanol and isopropanol; alkylene glycol monoethers such as ethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether; toluene and Aromatic compounds such as xylene; esters such as propylene glycol monomethyl ether acetate, ethyl acetate and butyl acetate; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; ethers such as dibutyl ether; diacetone alcohol; and N-methylpyrrolidone Can be mentioned. Among these, alkylene glycol monoethers such as propylene glycol monomethyl ether are particularly preferable because they are not only excellent in dispersibility or solubility of various components but also difficult to dissolve the resin member body to which the composition is applied.

  Furthermore, if an organic solvent that does not dissolve the resin member body such as alcohol or alkylene glycol monoether and an organic solvent that dissolves the resin member body such as ester or ketone are mixed and used as the organic solvent, In the subsequent heating process, the member main body is not melted, and the surface of the resin member main body is dissolved on the order of microns to increase the film adhesion. Moreover, the technique of improving the smoothness of the film | membrane surface is applicable by using together the organic solvent of various boiling points.

  As for the content rate of the organic solvent in the composition of this invention, 10-1000 mass parts is preferable with respect to a total of 100 mass parts of (A) component, (B) component, and (C) component. When the blending amount of the organic solvent is too small, it is difficult to uniformly apply the composition, and when it is too large, it is difficult to obtain a film having a sufficient thickness. Accordingly, the organic solvent may be appropriately selected according to the coating method, but if it is stipulated, it is preferably 50 to 500 parts by mass, more preferably 50 to 300 parts by mass from the viewpoint of productivity. .

  By using a hindered amine light stabilizer, the weather resistance of the film of the present invention can be improved. Any known hindered amine light stabilizer may be employed. A hindered amine light stabilizer may be used independently and may use 2 or more types together. As a content rate of a hindered amine light stabilizer, 0.05-1.5 mass parts is preferable with respect to a total of 100 mass parts of (A) component, (B) component, and (C) component, and 0.1-1 Part by mass is more preferable.

  Specific examples of the hindered amine light stabilizer include bis (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate and methyl (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate. 2,4-bis [N-butyl-N- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) amino] -6- (2-hydroxyethylamine) -1,3 , 5-triazine, decanedioic acid bis (2,2,6,6-tetramethyl-1- (octyloxy) -4-piperidinyl) ester. Among these, those having a low basicity of hindered amine are preferable from the viewpoint of the stability of the composition, and specifically, a so-called NOR type having an amino ether group is more preferable.

  Various surface modifiers may be added to the composition of the present invention for the purpose of increasing the leveling property at the time of coating, the purpose of increasing the slipping property of the film and improving the scratch resistance, and the like. As the surface modifier, various additives for modifying the surface physical properties, which are commercially available under the names of a surface conditioner, a leveling agent, a slipperiness imparting agent, an antifouling imparting agent and the like, can be used. Of these, silicone-based surface modifiers and fluorine-based surface modifiers are preferred.

  Specific examples include silicone polymers and oligomers having a silicone chain and a polyalkylene oxide chain, silicone polymers and oligomers having a silicone chain and a polyester chain, fluorine polymers and oligomers having a perfluoroalkyl group and a polyalkylene oxide chain, Examples thereof include fluorine-based polymers and oligomers having a perfluoroalkyl ether chain and a polyalkylene oxide chain. The above-mentioned silicone polymer and oligomer, fluorine polymer and oligomer may contain a carbon-carbon double bond in the chemical structure.

  A surface modifier may be used independently and may use 2 or more types together. You may use what contains a (meth) acryloyl group in a molecule | numerator for the objective of improving the sustainability of slipperiness.

  The preferable compounding amount of the surface modifier is 0.01 to 2 parts by mass, and 0.03 to 1 part by mass with respect to a total of 100 parts by mass of the component (A), the component (B), and the component (C). Is more preferable, and 0.05 to 0.5 parts by mass is particularly preferable. The surface smoothness of a film | membrane can be improved by the compounding quantity of a surface modifier being 0.01-2 mass parts.

  Specific surface modifiers include EBECRYL350 (Daicel Ornex Co., Ltd.), EBECRYL1360 (Daicel Ornex Co., Ltd.), BYK-315 (Bicchemy Japan Co., Ltd.), BYK-349 (Bicchemy Japan Co., Ltd.), BYK. -371 (Bic Chemie Japan Co., Ltd.), BYK-375 (Bic Chemie Japan Co., Ltd.), BYK-378 (Bic Chemie Japan Co., Ltd.), BYK-UV3500 (Bic Chemie Japan Co., Ltd.), BYK-UV 3570 (Bic Chemie Japan Co., Ltd.) Co., Ltd.), X-22-164 (Shin-Etsu Chemical Co., Ltd.), X-22-164AS (Shin-Etsu Chemical Co., Ltd.), X-22-164A (Shin-Etsu Chemical Co., Ltd.), X-22-164B (Shin-Etsu) Chemical industry stock Company), X-22-164C (Shin-Etsu Chemical Co., Ltd.), X-22-164E (Shin-Etsu Chemical Co., Ltd.), X-22-174DX (Shin-Etsu Chemical Co., Ltd.), X-22-2426 (Shin-Etsu Chemical) Industrial Co., Ltd.), X-22-2475 (Shin-Etsu Chemical Co., Ltd.), AC-SQ TA-100 (Toagosei Co., Ltd.), AC-SQ SI-20 (Toagosei Co., Ltd.), MAC-SQ TM-100 (Toagosei Co., Ltd.), MAC-SQ SI-20 (Toagosei Co., Ltd.), MAC-SQ HDM (Toagosei Co., Ltd.), Megafuck RS-75 (DIC Corporation), Megafuck RS-76-E ( DIC Corporation), Megafuck RS-72-K (DIC Corporation), Megafuck RS-76-NS (DIC Corporation), Megafuck RS-90 (DIC Corporation) Co., Ltd.), OPTOOL DAC-HP (Daikin Industries), ZX-058-A (T & K TOKA), ZX-201 (T & K TOKA), ZX-202 (T & K TOKA), ZX-212 ( T & K TOKA Co., Ltd.), ZX-214-A (T & K TOKA Co., Ltd.), and 8019 additive (Toray Dow Corning Co., Ltd.).

  A polymerization inhibitor is preferably added to the composition of the present invention for the purpose of improving storage stability. Specific examples of the polymerization inhibitor include hydroquinone, tert-butylhydroquinone, hydroquinone monomethyl ether, 2,6-di-tert-butyl-4-methylphenol, 2,4,6-tri-tert-butylphenol, benzoquinone, phenothiazine. N-nitrosophenylhydroxylamine, ammonium salt of N-nitrosophenylhydroxylamine, aluminum salt of N-nitrosophenylhydroxylamine, copper dibutyldithiocarbamate, copper chloride, copper sulfate.

  The addition amount of the polymerization inhibitor in the composition of the present invention is preferably 10 to 10,000 ppm, more preferably 100 parts by mass in total of the components (A), (B) and (C). Is 100 to 3000 ppm.

  Various antioxidants may be blended in the composition of the present invention for the purpose of improving the heat resistance and weather resistance of the film. Examples of the antioxidant include primary antioxidants such as hindered phenol antioxidants, and sulfur and phosphorus secondary antioxidants. A preferable blending amount of the antioxidant is 0 to 5 parts by mass, more preferably 0 to 3 parts by mass with respect to 100 parts by mass in total of the components (A), (B), and (C). .

  Specific examples of the primary antioxidant include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], ethylenebis (oxyethylene) bis [3- (5-tert- Butyl-4-hydroxy-m-tolyl) propionate], 1,3,5-tris [(4-tert-butyl-3-hydroxy-2,6-xylyl) methyl] -1,3,5-triazine-2 , 4, 6 (1H, 3H, 5H) -trione.

  Specific examples of secondary antioxidants include didodecyl 3,3′-thiodipropionate, 4,6-bis (octylthiomethyl) -o-cresol, tris (2,4-di-tert-butylphenyl) A phosphite can be illustrated.

  The composition of the present invention may contain an unsaturated compound having one or more radically polymerizable unsaturated groups in one molecule, which does not correspond to the component (A) and the component (B). As a compounding ratio of the unsaturated compound, from the viewpoint of preventing deterioration of wear resistance and weather resistance, 25 parts by mass or less with respect to a total of 100 parts by mass of the component (A), the component (B), and the component (C). Preferably, it is 15 parts by mass or less, more preferably 8 parts by mass or less, and particularly preferably 5 parts by mass or less. Moreover, as an example of the range of the compounding ratio of an unsaturated compound, 5-25 mass parts and 10-20 mass parts are made with respect to a total of 100 mass parts of (A) component, (B) component, and (C) component. Can be mentioned.

  The unsaturated compound includes a compound having one radical polymerizable unsaturated group in one molecule (hereinafter referred to as “monofunctional unsaturated compound”) and two or more radical polymerizable unsaturated groups in one molecule. (Hereinafter referred to as “polyfunctional unsaturated compound”).

  When a polyfunctional unsaturated compound is blended in the composition of the present invention, (A) with respect to a total of 100 parts by mass of the component (A), the component (B), the component (C) and the polyfunctional unsaturated compound. It is preferable that the component is 50 to 70 parts by mass, the component (B) is 5 to 40 parts by mass, the component (C) is 5 to 15 parts by mass, and the polyfunctional unsaturated compound is 5 to 25 parts by mass.

  A monofunctional unsaturated compound can be mix | blended in order to improve the adhesiveness of a film | membrane and a resin-made member main body. The radically polymerizable unsaturated group in the monofunctional unsaturated compound is preferably a (meth) acryloyl group.

  Specific examples of the monofunctional unsaturated compound include (meth) acrylic acid, Michael addition dimer of acrylic acid, ω-carboxy-polycaprolactone mono (meth) acrylate, monohydroxyethyl (meth) acrylate phthalate, methyl ( Of (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, (meth) acrylate of phenol alkylene oxide adduct, alkylphenol Alkylene oxide adduct (meth) acrylate, cyclohexyl (meth) acrylate, tert-butylcyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl Pyr (meth) acrylate, 4-hydroxybutyl acrylate, (meth) acrylate of alkylene oxide adduct of paracumylphenol, orthophenylphenol (meth) acrylate, (meth) acrylate of orthophenylphenol alkylene oxide adduct, tetrahydrofur Furyl (meth) acrylate, isobornyl (meth) acrylate, tricyclodecanemethylol (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, N- (2- (meth) acryloxyethyl) hexahydrophthalimide, N- (2- (meth) acryloxyethyl) tetrahydrophthalimide, N, N-dimethylacrylamide, acryloylmorpholine, N-vinylpyrrolidone, N-vinylcaprol An example is cutum.

  A polyfunctional unsaturated compound can be mix | blended in order to improve the adhesiveness of a film | membrane and a resin-made member main body, and the abrasion resistance of a film | membrane. The number of radically polymerizable unsaturated groups in the polyfunctional unsaturated compound is preferably 3 or more, more preferably 4 to 20 in one molecule so as not to lower the wear resistance. The polyfunctional unsaturated compound is preferably a compound having two or more (meth) acryloyl groups in one molecule. Specific examples thereof include tricyclodecane dimethylol di (meth) acrylate and ethylene glycol di (meth) acrylate. , Polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9- Nonanediol di (meth) acrylate, glycerin di (meth) acrylate, di (meth) acrylate of glycerol alkylene oxide adduct, dimer acid diol di (meth) acrylate, cyclohexanedimethylol di (meth) acrylate Trimethylolpropane tri (meth) acrylate, trimethylolpropane alkylene oxide adduct tri (meth) acrylate, pentaerythritol tri- or tetraacrylate, pentaerythritol alkylene oxide adduct tri- or tetraacrylate, ditrimethylolpropane tetra ( Examples include (meth) acrylate, dipentaerythritol hexa or pentaacrylate, polyester (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, and a silicone resin having a (meth) acryloyl group at the terminal.

  As a polyester (meth) acrylate, the dehydration condensate of a polyester polyol and (meth) acrylic acid is mentioned. Polyester polyols include low molecular weight polyols such as ethylene glycol, polyethylene glycol, cyclohexane dimethylol, 3-methyl-1,5-pentanediol, propylene glycol, polypropylene glycol, 1,6-hexanediol, and trimethylolpropane, and Examples include reactants from polyols such as these alkylene oxide adducts and acid components such as dibasic acids such as adipic acid, succinic acid, phthalic acid, hexahydrophthalic acid and terephthalic acid or anhydrides thereof. Moreover, the dehydration condensate of various dendrimer type polyols and (meth) acrylic acid is mentioned.

  Epoxy (meth) acrylates include (meth) acrylic acid adducts of phenol or cresol novolac type epoxy resins, (meth) acrylic acid adducts of biphenyl type epoxy resins, and diglycidyl ethers of polyethers such as polytetramethylene glycol. (Meth) acrylic acid adduct, (meth) acrylic acid adduct of polybutadiene diglycidyl ether, (meth) acrylic acid adduct of polybutadiene internal epoxidized product, (meth) acrylic acid adduct of silicone resin having epoxy group, Examples include a (meth) acrylic acid adduct of limonene dioxide and a (meth) acrylic acid adduct of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate.

  Examples of the urethane (meth) acrylate include compounds obtained by addition reaction of organic polyisocyanate and hydroxyl group-containing (meth) acrylate, and compounds obtained by addition reaction of organic polyisocyanate, polyol and hydroxyl group-containing (meth) acrylate. Examples of the organic polyisocyanate include tolylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate. Examples of the hydroxyl group-containing (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, hydroxyalkyl (meth) acrylate such as 4-hydroxybutyl (meth) acrylate, pentaerythritol tri ( Examples include hydroxyl group-containing polyfunctional (meth) acrylates such as (meth) acrylate and dipentaerythritol penta (meth) acrylate. Examples of the polyol include a low molecular weight polyol, a polyether polyol, a polyester polyol, and a polycarbonate polyol. Examples of the low molecular weight polyol include ethylene glycol, propylene glycol, neopentyl glycol, cyclohexane dimethylol, 3-methyl-1,5-pentanediol, and glycerin. Examples of the polyether polyol include polypropylene glycol and polytetramethylene glycol. As the polyester polyol, a reaction product of these low molecular weight polyol and / or polyether polyol and an acid component such as adipic acid, succinic acid, phthalic acid, hexahydrophthalic acid and terephthalic acid, or a dibasic acid or its anhydride. Is mentioned.

  Moreover, as a polyfunctional unsaturated compound, the compound represented by following General formula (5) can be mentioned.

In the general formula (5), R ⁷ , R ⁸ and R ⁹ each independently represent a divalent organic group having 2 to 10 carbon atoms. The divalent organic group having 2 to 10 carbon atoms is preferably an alkylene group having 2 to 4 carbon atoms such as ethylene group, trimethylene group, propylene group and tetramethylene group. Further, the general formula (5) also includes a compound modified with ε-caprolactone, in which case —COCH ₂ CH ₂ CH ₂ CH ₂ CH ₂ O— or —OCOCH ₂ CH ₂ CH ₂ CH ₂ CH ₂ — is substituted. , Between the isocyanuric ring and the (meth) acrylate group. Those in which R ⁷ , R ⁸ and R ⁹ are all ethylene groups are particularly preferred because a film having particularly excellent wear resistance and weather resistance can be obtained.

In the general formula (5), R ¹⁰ , R ¹¹ and R ¹² each independently represent hydrogen or a methyl group. Here, a compound in which R ¹⁰ , R ¹¹ and R ¹² are all hydrogen is particularly preferable in terms of excellent curability.

In the general formula ^{(5), n 1, n} 2 and ^{n 3} are each independently a number from 1-3. ^However, it is ^{n 1 + n 2 + n 3} = 3~9. The n ^{1, n 2} and ^{n 3,} 1 is ^preferred, as the ^{n 1 + n 2 + n 3} 3 are preferred. N ¹ , n ² and n ³ are the average moles of (O—R ⁷ ), (R ⁸ —O) and (R ⁹ —O) per mole of the compound represented by the general formula (5). Represents a number.

  The unsaturated compounds listed above may be used alone or in combination of two or more.

  An organic polymer can also be blended with the composition of the present invention for the purpose of reducing warpage during curing while maintaining transparency. Suitable polymers include (meth) acrylic polymers, and suitable constituent monomers include methyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acrylic acid, glycidyl (meth) acrylate, N- ( 2- (meth) acryloxyethyl) tetrahydrophthalimide and the like. In the case of a polymer copolymerized with (meth) acrylic acid, glycidyl (meth) acrylate may be added to introduce a (meth) acryloyl group into the polymer chain.

  The film of the present invention is obtained by curing the composition of the present invention containing the component (A), the component (B) and the component (C). When the composition of the present invention is cured, the component (A), the component (B) and the like undergo a polymerization reaction to become a polymer. Therefore, the film of the present invention contains a polymer obtained by polymerizing the polymerizable component contained in the composition of the present invention. The film of the present invention acts as a protective film for the resin member body by covering the surface of the resin member body.

  The film thickness of the film of the present invention will be described. The weather resistance improves as the film thickness increases. However, from the viewpoint of the appearance and productivity of the film, it is not preferable to increase the film thickness significantly. In consideration of weather resistance, appearance, and productivity, the film thickness is preferably 5 to 70 μm, more preferably 10 to 50 μm. The film of the present invention exhibits excellent adhesion without forming an undercoat layer between the film and the resin member body.

The resin member of the present invention comprises a resin member body having a repeating unit represented by the following general formula (4), and the film of the present invention covering the resin member body. .
^{- (A 2 -CO) - ...} (4)
(In the general formula (4), ^{A 2} is represented by the following general formula (4-1).)

In General Formula (4-1), R ⁴¹ and R ⁴² each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, or a phenyl group. Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, an n-propyl group, and an i-propyl group. R ⁴¹ and R ⁴² are preferably substituted at the 2-position of the benzene ring as viewed from the substitution position of O on the benzene ring.

B ² represents CR ⁴³ R ⁴⁴ , SO ₂ , C═CX ₂ , and the following general formula (4-2). R ⁴³ and R ⁴⁴ each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, an X-substituted alkyl group having 1 to 6 carbon atoms, or a phenyl group. Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, and an n-propyl group. X means halogens such as fluorine and chlorine. Examples of the X-substituted alkyl group having 1 to 6 carbon atoms include CH ₂ F, CHF ₂ , CF ₃ , CH ₂ CF ₃ , and C ₂ F ₅ .

R ⁴³ and R ⁴⁴ can form a saturated hydrocarbon ring that can be alkyl-substituted together with carbons bonded to each other. Examples of saturated hydrocarbon rings that can be substituted with alkyl include cyclopentane ring, cyclohexane ring, cycloheptane ring, 3,3-dimethylcyclohexane ring, 3,5-dimethylcyclohexane ring, and 3,3,5-trimethylcyclohexane ring. .
Examples of C = CX ₂ include C = CF ₂ , C = CCl ₂ , and C = CBr ₂ .
General formula (4-2) is as follows.

In General Formula (4-2), R ⁴⁵ , R ⁴⁶ , R ⁴⁷ and R ⁴⁸ each independently represent hydrogen or an alkyl group having 1 to 6 carbon atoms. Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, and an n-propyl group. The substitution positions of R ⁴⁵ R ⁴⁶ C and CR ⁴⁷ R ⁴⁸ with respect to the benzene ring are preferably meta or para positions.

The specific chemical structure of A ² is the same as that listed for A ¹ .

Resin member body having a repeating unit represented by the general formula (4), the A ² derivative and CO derivative, can be produced by causing appropriate reaction. For example, HA ² H may be employed as the A ² derivative, phosgene may be employed as the CO derivative, and these may be reacted to produce. Moreover, in order to obtain this resin member main body, you may purchase resin which has a repeating unit represented by the said General formula (4) marketed.

Since the chemical structure of the component (B) contained in the composition of the present invention is similar to the chemical structure of the repeating unit represented by the general formula (4) contained in the resin member body, the film of the present invention It is considered that the affinity between the resin member body increases and the adhesion between the membrane of the present invention and the resin member body increases. From this consideration, it is considered that a resin member having a combination in which the chemical structure of the component (B) and the chemical structure of the repeating unit represented by the general formula (4) are more similar is most preferable. Then, the chemical structures of A ¹ included in the film of the present invention, the resin member chemical structure of A ² are the same contained in the resin member body, it can be said that most excellent in adhesion.

  The resin member main body in the resin member of the present invention is covered with the film of the present invention. The covering portion may be a partial surface of the resin member main body or the entire surface. What is necessary is just to coat | cover the film | membrane of this invention with the appropriate quantity suitably in the location where abrasion resistance and a weather resistance are requested | required among resin member main bodies.

  Applications of resin members include automobile materials such as automobiles, industrial vehicles, personal vehicles, self-propelled car bodies, interior and exterior members for vehicles such as railways, exterior plates for vehicles, and resin windows for vehicles. And materials for construction, materials for playground equipment, materials for civil engineering, materials for household appliances, materials for medical equipment, materials for communication equipment, materials for stationery, and materials for protective equipment.

  Describing in detail the vehicle material, examples of the vehicle exterior member include a door molding, a frame frame of a door mirror, a wheel cap, a spoiler, a bumper, a winker lens, a pillar garnish, a rear finisher, a head lamp cover, and the like.

  Examples of vehicle interior members include instrument panels, console boxes, meter covers, door lock pels, steering wheels, power window switch bases, center clusters, dashboards, and bonnets.

  Examples of the vehicle outer plate include a front fender, a door panel, a roof panel, a hood panel, a trunk lid, and a back door panel.

  Examples of the vehicle resin window include a sunroof, a windshield, a side glass, a rear glass, a rear water glass, and a rear door water glass.

  Below, the manufacturing method of the composition of this invention, a film | membrane, and a resin-made member is demonstrated. The method for producing a film and a resin member of the present invention mainly includes a preparation step, a coating step, and a curing step.

  The preparation step is a step of preparing the composition of the present invention by mixing each component at a predetermined blending ratio.

  An application process is a process of apply | coating the composition of this invention to at least one part of the surface of a resin-made member main body. The method for applying the composition may follow a conventional method. For example, a spray method, a spin coat method, a dip coat method, a bar coat method, a flow coat method and the like are preferable, and may be selected according to the shape of the resin member body. At this time, if the surface of the resin member main body is not exposed to the composition containing the organic solvent for a long time, deterioration of the resin member main body due to the organic solvent is suppressed. Although the film thickness of the coating film formed by application depends on the ratio of the solid content contained in the composition, it may be appropriately selected according to the thickness of the obtained film. For example, the film thickness of the coating film (before drying and curing) is preferably 6 to 100 μm. If the film thickness after drying or curing is insufficient, the steps from application to curing may be repeated.

  You may perform the drying process which dries a coating film between an application | coating process and a hardening process. A drying process is a process of removing volatile components, such as an organic solvent and water, by means, such as natural drying, heat drying, and vacuum drying. What is necessary is just to select the drying temperature of a coating film suitably according to the heat resistance of a resin-made member main body, and, specifically, it is preferable to make drying temperature into the range of 50-120 degreeC.

  The curing step is a step of curing the composition (coating film) to form a film on the surface of the resin member body. Since at least the component (A) and the component (B) in the composition contain polymerizable terminal olefin, the polymerization reaction proceeds by applying energy such as heat to the composition, and the composition is cured. When the composition contains a photo radical polymerization initiator or a thermal radical polymerization initiator, the composition may be subjected to conditions under which each polymerization initiator acts. When the composition contains a radical photopolymerization initiator, the composition is applied to the resin member body, dried, and then irradiated with light such as ultraviolet rays. As a preferable production method, a method of irradiating the dried coating film with light under high temperature conditions can be mentioned. Here, the high temperature condition may be equal to or lower than the performance maintaining temperature of the resin member body. For example, the range of 50-120 degreeC is preferable, the range of 60-110 degreeC is more preferable, the range of 70-100 degreeC is further more preferable, and the range of 80-100 degreeC is especially preferable. Abrasion resistance of the film can be enhanced by maintaining the temperature condition when irradiating with ultraviolet rays in the range of 50 to 120 ° C.

Examples of light include ultraviolet light and visible light, and ultraviolet light is particularly preferable. Examples of the ultraviolet irradiation device include a high-pressure mercury lamp, a metal halide lamp, a UV electrodeless lamp, and an LED. In the case of a UV electrodeless lamp, a new type using a DC power supply current can also be suitably used. Irradiation energy should be appropriately set according to the type and composition of the active energy ray. As an example, when a high-pressure mercury lamp is used, the irradiation energy in the UV-A region is 100 to 10,000 mJ / cm ² is preferable, and 1,000 to 6,000 mJ / cm ² is more preferable.

  When the composition contains a thermal radical polymerization initiator, the composition is applied to the resin member body, dried, and further heated. Although it will not specifically limit as heating temperature if it is below the performance maintenance temperature of a resin-made member main body, 80-200 degreeC is preferable. As heating time, 10 minutes or more and 120 minutes or less are preferable. From the viewpoint of productivity, the time is preferably 60 minutes or less, more preferably 30 minutes or less.

  The curing step may be performed in the air or in a vacuum or in an inert gas atmosphere. In view of the performance of the film, it is preferably in a vacuum or in an inert gas atmosphere, but may be performed in the air from the viewpoint of productivity.

  In this specification, the temperature of drying and heating is the surface temperature of the coating film, and is approximately equal to the atmospheric temperature of drying or heating.

  As mentioned above, although embodiment of this invention was described, this invention is not limited to the said embodiment. The present invention can be implemented in various forms without departing from the gist of the present invention, with modifications and improvements that can be made by those skilled in the art.

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. In addition, this invention is not limited by these Examples. Hereinafter, “parts” means parts by mass, and “%” means mass%.

(Production Example 1): Production of component (A) (HDI3-HBA)
Into a 3 L separable flask equipped with a stirrer and an air blowing tube, an isocyanate compound having a nurate trimer of hexamethylene diisocyanate as a main component [Duranate TPA-100 manufactured by Asahi Kasei Chemicals Corporation. NCO content 23%. ] 1369.5 g (NCO 7.5 mol), 2,6-di-tert-butyl-4-methylphenol 1.22 g, and dibutyltin dilaurate 0.73 g were added, while stirring at a liquid temperature of 50 to 70 ° C., 4 -1080 g (7.5 mol) of hydroxybutyl acrylate was added dropwise.

  After completion of dropping, the mixture was stirred at 80 ° C. for 4 hours, and the reaction was terminated by confirming that the isocyanate group disappeared from the reaction solution by IR analysis. The isocyanuric ring-containing urethane corresponding to component (A) An acrylate compound was obtained. Hereinafter, this reaction product is referred to as “HDI3-HBA”.

HDI3-HBA corresponds to a compound in which R ¹ , R ² and R ³ are all tetramethylene groups and R ⁴ , R ⁵ and R ⁶ are all hydrogen in the general formula (1).

(Production Example 2): Production of component (C) (THPI-silica)
A 3 L separable flask equipped with a stirrer was charged with 1119 g of toluene and 456 g (3.0 mol) of 3,4,5,6-tetrahydrophthalic anhydride, and stirred at room temperature under nitrogen with 3-aminopropyltrimethyl trichloride. 663 g (3.0 mol) of ethoxysilane was added dropwise. After completion of the dropwise addition, the temperature was raised until ethanol was distilled off, and then the reaction solution was allowed to react for 4 hours while maintaining the reaction solution in the range of 85 to 110 ° C.

After completion of the reaction, the low boiling point components such as toluene and ethanol were distilled off under reduced pressure while heating the flask in an oil bath at 80 ° C. to obtain a compound corresponding to (c1) which is a silane compound of the general formula (3). Hereinafter, this reaction product is referred to as “THPI-alkoxysilane”. From the ¹ H-NMR spectrum, the structure of the obtained THPI-alkoxysilane is as follows. In the general formula (3), R ¹³ is an ethyl group, R ¹⁴ is a 1,3-propylene group (trimethylene group), and z is 1. 2 was confirmed.

  In a 3 L separable flask equipped with a stirrer, 960 g of propylene glycol monomethyl ether (hereinafter referred to as PGM), 23.6 g of water, and isopropyl alcohol-dispersed colloidal silica (IPA-ST manufactured by Nissan Chemical Industries, Ltd., average particle size 10 ˜15 nm (value calculated from specific surface area by BET method), solid content 30%, isopropyl alcohol 70% contained.) After stirring and homogenizing, 189 g of THPI-alkoxysilane was charged and stirred at room temperature, colloidal dispersion Liquid. At this time, the mass ratio of (c1) to (c2) was 44:56.

  This colloidal dispersion was heated to 80 ° C. under nitrogen and reacted for 4 hours, and then concentrated by distilling off IPA, water and the like until the non-volatile components were 35%. Next, 640 g of PGM was added, and a small amount of water remaining in the reaction system was distilled off together with PGM and the like to obtain a reaction product having a nonvolatile component of 35%. Hereinafter, among the reaction products obtained here, the non-volatile component (component (C)) excluding the solvent and the like is referred to as “THPI-silica”.

Example 1
As the component (B), in general formula (2), R ²¹ and R ²² are hydrogen, R ²³ and R ²⁴ are ethylene groups, m + n is 3, A ¹ is represented by general formula (2-1), and R The diacrylate compound represented by ²⁵ and R ²⁶ is hydrogen and B ¹ is C (CH ₃ ) ₂ , and the composition, film, and resin member of Example 1 were produced as follows.

  60 parts of HDI3-HBA as component (A), 30 parts of the diacrylate compound as component (B), 10 parts of THPI-silica as component (C), Irg-819 as a radical photopolymerization initiator (BASF Corporation) , 2 parts of the trade name Irgacure 819), 5 parts of RUVA-93 (Otsuka Chemical Co., Ltd.) as an ultraviolet absorber, 110 parts of propylene glycol monomethyl ether as an organic solvent, and T-123 (BASF shares as a hindered amine light stabilizer) Company, trade name: Tinuvin 123) 0.5 parts and 8019 additive (Toray Dow Corning Co., Ltd.) 0.1 parts as a surface modifier were mixed and stirred to give the composition of Example 1.

Irg-819 is bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide. RUVA-93 is 2- [2-hydroxy-5- (2-methacryloyloxyethyl) phenyl] -2H-benzotriazole. T-123 is decanedioic acid bis (2,2,6,6-tetramethyl-1- (octyloxy) -4-piperidinyl) ester. 8019additive contains about 99% octamethylcyclotetrasiloxane as a surface modifier.
For reference, the chemical structures of RUVA-93 and T-123 are shown below.

As the resin member main body, A ^{2 in the} general formula (4) is represented by the general formula (4-1), R ⁴¹ and R ⁴² are hydrogen, and B ² is a resin represented by C (CH ₃ ) _2. A plate cut to a size of 10 cm × 10 cm was prepared.

  The composition of Example 1 was applied to the surface of the resin member main body with a bar coater so that the coating thickness after drying was about 15 to 35 μm. Next, after drying with a hot air dryer at 100 ° C. for 10 minutes, UV irradiation was immediately performed (at a coating film surface temperature of 90 ° C.), and the film of Example 1 (film thickness: 14 μm) was formed on the surface of the resin member body. The resin-made member of Example 1 provided with this was produced.

UV irradiation uses a high-pressure mercury lamp manufactured by Eye Graphics Co., Ltd., and has a peak illumination intensity of 400 mW / cm ² and an irradiation energy of 250 mJ / cm ^{2 in} one pass in the UV-A region of UV POWER PUCK manufactured by EIT. The lamp output, the lamp height, and the conveyor speed were adjusted so as to satisfy the following conditions, and irradiation was performed for 12 passes (total 3000 mJ / cm ² ).

(Example 2)
(B) The composition of Example 2 was the same as Example 1 except that a diacrylate compound having the same chemical structure as that of Component (B) of Example 1 was employed except that m + n was 4. Articles, membranes and resin members were manufactured.

(Example 3)
The composition of Example 3 was the same as Example 1 except that a diacrylate compound having the same chemical structure as the component (B) of Example 1 was employed as the component (B) except that m + n was 10. Articles, membranes and resin members were manufactured.

Example 4
The composition of Example 4 was the same as Example 1 except that a diacrylate compound having the same chemical structure as that of Component (B) in Example 1 was employed as the component (B) except that m + n was 17. Articles, membranes and resin members were manufactured.

(Example 5)
The composition of Example 5 was the same as that of Example 1 except that a diacrylate compound having the same chemical structure as that of component (B) of Example 1 was employed as the component (B) except that m + n was 30. Articles, membranes and resin members were manufactured.

(Example 6)
Example except that 10 parts of the diacrylate compound used in Example 3 as component (B) and 20 parts of M-315 (Toagosei Co., Ltd., trade name Aronix M-315) as component (B ′) were used. In the same manner as in Example 1, the composition, membrane and resin member of Example 6 were produced.

  The component (B ′) is a compound that does not correspond to the component (B) and has a plurality of acrylate groups like the component (B), that is, one embodiment of a polyfunctional unsaturated compound.

M-315 is tris (acryloyloxyethyl) isocyanurate, and in the general formula (5), R ⁷ , R ⁸ and R ⁹ are ethylene groups, R ¹⁰ , R ¹¹ and R ¹² are hydrogen, It corresponds to a compound in which n ¹ , n ² and n ³ are 1 and n ¹ + n ² + n ³ = 3.

(Example 7)
Example except that 20 parts of the diacrylate compound used in Example 3 was used as the component (B) and 10 parts of M-315 (Toagosei Co., Ltd., trade name Aronix M-315) was used as the component (B ′). 1 was used to produce the composition, membrane and resin member of Example 7.

(Example 8)
Example except that 10 parts of the diacrylate compound used in Example 4 as component (B) and 20 parts of M-315 (Toagosei Co., Ltd., trade name Aronix M-315) were used as component (B ′) 1 was used to produce the composition, membrane and resin member of Example 8.

Example 9
Example except that 20 parts of the diacrylate compound used in Example 4 was employed as the component (B) and 10 parts of M-315 (Toagosei Co., Ltd., trade name Aronix M-315) was employed as the component (B ′). 1 was used to produce the composition, membrane and resin member of Example 9.

(Comparative Example 1)
The composition, film and resin member of Comparative Example 1 were produced in the same manner as in Example 1, except that the component (B) was not employed and 90 parts of HDI3-HBA was employed as the component (A).

(Comparative Example 2)
A comparative example is the same as in Example 1 except that (B) component is not employed and 30 parts of M-315 (Toagosei Co., Ltd., trade name Aronix M-315) is employed as the component (B ′). 2 composition, membrane and resin member were produced.
The composition of Comparative Example 2 corresponds to the composition specifically disclosed in Patent Document 2.

(Comparative Example 3)
The composition of Comparative Example 3 was the same as Example 1 except that (B) component was not employed and 30 parts of A-9300-1CL (Shin Nakamura Chemical Co., Ltd.) was employed as component (B ′). Articles, membranes and resin members were manufactured.

A-9300-1CL is ε-caprolactone-modified tris (acryloyloxyethyl) isocyanurate, and-(COCH ₂ CH ₂ CH ₂ CH ₂ CH between the acryloyl group and the oxyethylene group of M-315, respectively. ₂ O) ₁ -group,-(COCH ₂ CH ₂ CH ₂ CH ₂ CH ₂ O) _m -group,-(COCH ₂ CH ₂ CH ₂ CH ₂ CH ₂ O) _n -group inserted in l + m + n = 1 It corresponds to.

(Comparative Example 4)
Comparative Example 4 was carried out in the same manner as in Example 1 except that (B) component was not employed and 30 parts of tricyclodecane dimethanol diacrylate (hereinafter abbreviated as TDD) was employed as component (B ′). A composition, a film and a resin member were prepared.

(Comparative Example 5)
In the same manner as in Example 1, except that (B) component was not used and 30 parts of neopentyl glycol hydroxypivalate ester diacrylate (hereinafter abbreviated as HPNDA) was used as component (B ′), The composition, membrane and resin member of Example 5 were produced.

The chemical structure of HPNDA is as follows.
_{CH 2 = CHCOOCH 2 C (CH} 3) 2 CH 2 COOCH 2 C (CH 3) 2 CH 2 OCOCH = CH 2
(Comparative Example 6)
The composition of Comparative Example 6 was prepared in the same manner as in Example 1, except that (B) component was not used and 30 parts of dioxane glycol diacrylate (hereinafter abbreviated as DDA) was used as component (B ′). A membrane and a resin member were manufactured.

  Dioxane glycol means 2- (1,1-dimethyl-2-hydroxyethyl) -5-ethyl-5-hydroxymethyl-1,3-dioxane.

(Comparative Example 7)
The composition of Comparative Example 7 was the same as Example 1 except that (B) component was not employed and 30 parts of APG-200 (Shin Nakamura Chemical Co., Ltd.) was employed as component (B ′). A membrane and a resin member were manufactured.

APG-200 is tripropylene glycol diacrylate, and its chemical structure is CH ₂ ═CHCOO (CH (CH ₃ ) CH ₂ O) _m (CH ₂ CH (CH ₃ ) O) _n COCH═CH _2. (M + n = 3).

(Comparative Example 8)
(B) The component, the film of Comparative Example 8, and the membrane of Comparative Example 8 were used in the same manner as in Example 1 except that 30 parts of M-305 (Toagosei Co., Ltd.) was used as the component (B ′) without adopting the component. A resin member was manufactured.

  M-305 is a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate, and the content of pentaerythritol triacrylate is 55 to 63%.

(Comparative Example 9)
(B) The component, the film of Comparative Example 9, and the film of Comparative Example 9 were used in the same manner as in Example 1 except that 30 parts of M-306 (Toagosei Co., Ltd.) was used as the component (B ′) without adopting the component. A resin member was manufactured.

  M-306 is a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate, and the content of pentaerythritol triacrylate is 65 to 70%.

(Evaluation example 1)
The following weather resistance test, appearance test, transparency test, and adhesion test were performed on the films and resin members of Examples 1 to 9 and Comparative Examples 1 to 9. The result of each test is shown in FIG.3 and FIG.4 with (A) component of each composition, (B) component, (C) component, and these compounding quantities.

Weather resistance test: In accordance with ISO 4892-2, an accelerated test for 10,000 hours was performed with a weather meter (xenon light source), and the following adhesion test was performed every 500 hours. 3 and 4 is the number of hours in which the film is peeled from the resin member body together with the cellophane tape when the cellophane tape is peeled off after the cellophane tape is applied to the film in the adhesion test. In FIG. 3 and FIG. 4, “> 10000 hours” is indicated when the film was not peeled off in the adhesion test after 10000 hours.
Accelerated test conditions Test cycle: One cycle of 102 minutes of light irradiation and 18 minutes of light irradiation and water spray was repeated.
Illuminance and control wavelength: 60 W / m ² , 300 to 400 nm
Temperature: 65 ± 3 ° C
Humidity: 50 ± 5% R.D. H.

  Appearance test: The properties of the film in the initial state were visually observed. In FIG. 3 and FIG. 4, those with good appearance are represented by “◯”, and those in which white turbidity is observed are represented by “Δ”.

  Transparency test: Haze H (%) of the film was measured with a turbidimeter NDH-2000 (manufactured by Nippon Denshoku Industries Co., Ltd.) according to JIS K7136 for each resin member in the initial state. The smaller the value of H, the better the transparency.

  Adhesion test: Cuts of 2 mm intervals, 11 in each length and width, were made in the film with a cutter knife to form 100 square grids. Cellophane tape (Nichiban Co., Ltd.) was applied to this grid, and the cellophane tape was peeled off according to JIS K5600. In FIG. 3 and FIG. 4, “O” represents that the film was not peeled off from the resin member main body together with the cellophane tape.

  As shown in FIG.3 and FIG.4, all the resin-made members of Examples 1-9 showed remarkably good weather resistance compared with the resin-made members of Comparative Examples 1-9. Due to the presence of the component (B), it was proved that the weather resistance of the resin member was remarkably improved. In particular, the weather resistance of the resin members of Examples 3 to 9 was remarkable.

  The component (B ′) of Comparative Examples 2 to 9 had a plurality of acrylate groups in the same manner as the component (B). Although the weather resistance of the resin-made members of Comparative Examples 2-9 was superior to the weather resistance of the resin-made members of Comparative Example 1, it did not reach the weather resistance of the resin members of Examples 1-9.

It can be considered that the similarity between the chemical structure of the membrane and the chemical structure of the resin member body has influenced the weather resistance of the resin member. In the present invention, the chemical structures of A ¹ included in the di (meth) acrylate compound represented by (B) the general formula of component (2), the chemical structure of A ² contained in the resin member body, to some extent , In a similar category. Therefore, no matter which one of the di (meth) acrylate compounds represented by the general formula (2) is selected as the component (B) and any of the repeating units represented by the general formula (4) is selected as the resin member body, It can be recognized that a resin member exhibiting a certain level of excellent weather resistance can be obtained.

  Regarding the appearance test, the transparency test, and the adhesion test, satisfactory results were obtained for the films and resin members of Examples 1 to 9 and Comparative Examples 1 to 9. If the compounding quantity of (A) component, (B) component, and (C) component is the range of the composition grade of Examples 1-9, it has confirmed that there was no problem in an external appearance, transparency, and adhesiveness.

(Application 1)
A specific example in which the resin member of the present invention is used as an automobile window glass (sunroof) will be described with reference to FIGS. FIG. 1 is a perspective view schematically showing a sunroof. The sunroof includes a window glass 1 and a frame-like frame 4 that supports the peripheral edge of the window glass 1. A loop-shaped weather strip 5 made of a flexible material is attached to the peripheral portions of the window glass 1 and the frame 4 in order to ensure airtightness in the vehicle. This sunroof is provided in an opening formed in the roof panel of the automobile so as to be freely opened and closed.

  FIG. 2 is a cross-sectional view schematically showing the window glass 1. The window glass 1 is composed of a glass main body 2 that is a resin member main body, and a film 3 of the present invention formed on at least a vehicle outer surface of the glass main body 2. The film 3 is formed by curing any of the compositions of the present invention according to the above procedure.

Claims (5)

20-80 parts by mass of the (A) component, 5-50 parts by mass of the (B) component, and 100 parts by mass of the following (A) component, (B) component, and (C) component. C) A composition comprising 1 to 35 parts by mass of a component.
(A) component:
Isocyanuric ring-containing urethane (meth) acrylate compound represented by the general formula (1)

(In General Formula (1), R ¹ , R ² and R ³ each independently represents a divalent organic group having 2 to 10 carbon atoms, and R ⁴ , R ⁵ and R ⁶ are each independently hydrogen or Represents a methyl group.)
(B) component:
Di represented by the serial general formula (2) (meth) acrylate compound _{^{CH 2 = CR 21 CO- (OR}} 23) m -A 1 - (R 24 O) n -COCR 22 = CH 2 ... (2)
(In the general formula (2), R ²¹ and R ²² each independently represent hydrogen or a methyl group, R ²³ and R ²⁴ each independently represent a divalent hydrocarbon group having 2 to 10 carbon atoms, m and n each independently represents an integer of 0 or more, and A ¹ is represented by the following general formula (2-1).

(In General Formula (2-1), R ²⁵ and R ²⁶ each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, or a phenyl group. B ¹ represents CR ²⁷ R ²⁸ , SO ₂ , C = CX ₂ represents the following general formula (2-2): R ²⁷ and R ²⁸ each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, an X-substituted alkyl group having 1 to 6 carbon atoms, or a phenyl group. X represents halogen, or R ²⁷ and R ²⁸ together with the carbons attached to each other form a saturated hydrocarbon ring that can be alkyl substituted.)

(In general formula (2-2), R ²⁹ , R ³⁰ , R ³¹ and R ³² each independently represent hydrogen or an alkyl group having 1 to 6 carbon atoms.)
Component (C):
A reaction product obtained by reacting the silane compound (c1) represented by the general formula (3) with the colloidal silica (c2) at a mass ratio of (c1) to (c2) of 9: 1 to 1: 9. Nonvolatile components, including those obtained by chemically modifying (c2) with (c1).

(In General Formula (3), R ¹³ represents hydrogen or a monovalent organic group, R ¹⁴ represents a divalent hydrocarbon having 1 to 6 carbon atoms, and z is a positive number of 0.1 or more and 3 or less. In addition, when z is less than 3, (c1) contains a condensate, and R ^{13 in} one molecule of the condensate may contain two or more different groups.   The composition according to claim 1, wherein in the general formula (2), m + n is in the range of 10-30.   A film obtained by curing the composition according to claim 1 or 2. A resin member comprising: a resin member main body having a repeating unit represented by the following general formula (4); and the film according to claim 3 covering the resin member main body.
^{- (A 2 -CO) - ...} (4)
(In the general formula (4), ^{A 2} is represented by the following general formula (4-1).)

(In General Formula (4-1), R ⁴¹ and R ⁴² each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, or a phenyl group. B ² represents CR ⁴³ R ⁴⁴ , SO ₂ , C = CX ₂ represents the following general formula (4-2): R ⁴³ and R ⁴⁴ each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, an X-substituted alkyl group having 1 to 6 carbon atoms, or a phenyl group. X represents halogen, or R ⁴³ and R ⁴⁴ together with the carbons attached to each other form a saturated hydrocarbon ring that can be alkyl substituted.)

(In the general formula (4-2), R ⁴⁵ , R ⁴⁶ , R ⁴⁷ and R ⁴⁸ each independently represent hydrogen or an alkyl group having 1 to 6 carbon atoms.) And chemical structures of A ¹ contained in the film, the resin member according to claim 4 chemical structure of A ² are the same contained in the resin member body.

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