JPH0686581B2 - Paint composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an active energy ray-curable coating composition containing a specific modified block copolymer. More specifically, it has excellent active energy ray curing properties in air, and in addition to chemical resistance, abrasion resistance, abrasion resistance, etc., improved non-adhesiveness for balance by including a specific modified block copolymer. The present invention relates to a coating composition capable of forming a crosslinked cured coating having excellent coating properties such as stain resistance, water / oil repellency, weather resistance, and adhesion.

[Prior art and its problems]

Generally, synthetic resin molded products such as thermoplastic resins have various advantages such as light weight and easy moldability, and are useful for cameras, lighting equipment, automobiles, household appliances, daily necessities, Widely used in many other fields. However, since the synthetic resin molded product has a low surface hardness, it may come into contact with other objects at the time of use, or the surface may be damaged or aesthetically damaged due to the action of scratching or the like. At times, when the molded product is used as an optical lens, a decorative case, a mirror, a reflecting mirror, a window glass, etc., its commercial value is remarkably reduced or it becomes unusable in a short period of time.

Many proposals have been made as methods for improving the drawbacks of these synthetic resin molded products. For example, JP-A-53-102936 discloses a specific polyfunctional (meth) acrylate having three or more (meth) acryloyloxy groups in one molecule such as pentaerythritol tetraacrylate and a specific polyfunctional (meth) acrylate.
A method is disclosed in which a coating film containing a mixture of functional (meth) acrylates as a main component is formed on the surface of a synthetic resin molded article, and the surface of the molded article is coated with a crosslinked cured coating by irradiating a high pressure mercury lamp or the like while circulating nitrogen gas. ing. JP-A-53-104638 and JP-A-54-97633 disclose a mixture of the specific other functional (meth) acrylate and the specific bifunctional (meth) acrylate, and / or the specific monofunctional (meth) acrylate. There is disclosed a method of forming a coating film containing as a main component in the same manner and irradiating a high pressure mercury lamp in an air atmosphere to form a crosslinked cured coating film. Further, as an improvement method thereof, JP-A-56-55464 discloses a method for improving wear resistance under a low load by adding a small amount of a specific linear higher fatty acid alkyl ester, JP-A-99238, a method of reducing the curability variation in an air atmosphere by using a photosensitizer having a specific structure, JP-A-56-
No. 122840 discloses that by blending a specific alkyl (meth) acrylate homopolymer or copolymer, an ultraviolet absorber and a photosensitizer in a specific ratio, the weather resistance and the abrasion resistance are improved. JP-A-57-128755 discloses a compound having a (meth) acrylamide group and a hydroxyl group, a liquid organic acid substituted with fluorine, chlorine and bromine at room temperature and atmospheric pressure and a photosensitizer. The method of improving adhesion to a cross-linking curable resin such as polydiethylene glycol bisallyl carbonate resin by blending in a ratio of, in JP-A-58-101120, a solution containing an alkali metal hydroxide. By pretreatment, a method of improving adhesion to the same cross-linking curable resin, such as abrasion resistance by coating a cross-linking cured film on the surface of a synthetic resin molded article,
A method for improving abrasion resistance and chemical resistance is disclosed.
Similarly, in JP-A-59-51908, a coating having excellent cross-linking curability, which is composed mainly of a mixture of a specific polyfunctional urethane (meth) acrylate and a reactive monomer, is formed on the surface of a synthetic resin molded product. By irradiating a low-pressure mercury lamp in the air to form a cross-linked cured coating with excellent adhesion, surface hardness, flexibility and durability with molded products, the surface of synthetic resin molded products is improved in scratch resistance, chemical resistance, etc. A method of doing so is disclosed.

In addition, JP-A Nos. 53-2567, 55-2611, and 56-
139507, 59-41366, 59-84926, 59-86631, 59-86666, 59-86.
No. 667, No. 59-86331, No. 59-89332,
No. 59-41366, No. 59-204624 and the like, urethane-based poly (meth) acrylate, epoxy-based poly (meth) acrylate, polyol-based poly (meth) acrylate, polyester-based poly (meth) acrylate,
A curable resin composition for coating such as melamine-based poly (meth) acrylate is disclosed.

However, although the coating composition for coating improves chemical resistance, scratch resistance, abrasion resistance, and abrasion resistance of the surface of the synthetic resin molded product, it has stain resistance, non-adhesiveness, water and oil repellency, etc. Has not been improved at all. In recent years, synthetic resin moldings are being developed for various purposes. Improving the chemical resistance and scratch resistance of synthetic resin moldings as well as stain resistance, non-adhesiveness and water / oil repellency. Required to do so.

In particular, in applications such as optical discs, window glass for automobiles, television front plates, and illuminator covers, there is a strong demand for imparting these performances in good balance at the same time.

JP-A-56-861 discloses a method in which non-adhesiveness, water / oil repellency and stain resistance may be simultaneously improved in addition to chemical resistance and scratch resistance of the surface of a synthetic resin molded article. Includes a specific polyfunctional (meth) acrylate having three or more (meth) acryloyloxy groups in one molecule such as pentaerythritol tetraacrylate and at least one ether bond in one molecule, and has a boiling point of A small amount of a silicone-based surfactant having a specific structure is added to a coating composition whose main component is a mixture with a monofunctional (meth) acrylate having a viscosity of 20 centipoise or less at 20 ° C at 150 ° C or higher. Accordingly, in addition to chemical resistance, abrasion resistance, etc., surface smoothness, prevention of whitening during film curing, and defoaming effect during the film coating process are disclosed.
Similarly, in JP-A-56-127635 and JP-A-56-141309, a silicon-based surfactant and a UV absorber having a specific structure or a hindered amine and a photosensitizer having a specific structure are limited to specific ratios. Discloses a method of improving weather resistance in addition to chemical resistance, abrasion resistance and the like. However, these methods have hardly improved in non-adhesiveness, water / oil repellency, and stain resistance.

On the other hand, JP-A-57-14648 and JP-A-57-192445 propose a method of adding a (per) fluoroalkyl group-containing surfactant to a vinyl chloride resin.

JP-A-58-34866 and JP-A-58-34867 disclose random copolymers composed of a (meth) acrylic acid ester containing a (per) fluoroalkyl group and a vinyl type monomer copolymerizable therewith. It is disclosed that the polymer forms a coating film excellent in weather resistance, water and oil repellency, and stain resistance.

Furthermore, Polymer Bulletin, VoL.5,3
35 (1981) and JP-A-57-179246, a graft copolymer obtained by grafting an alkyl ester polymer having a perfluoroalkyl group on the trunk of polymethylmethacrylate is added to polymethylmethacrylate. Thus, a method of imparting water and oil repellency to the surface is disclosed. JP-A-60-221410 discloses a block composed of a polymer block having a (per) fluoroalkyl group or a (per) fluoroalkylene group and a polymer block miscible with the resin to be modified. A method of imparting non-adhesiveness, water / oil repellency, stain resistance, weather resistance and the like to a surface by coating or adding a polymer to a target resin is disclosed.

However, the surface modification method described above has the following drawbacks. That is, in the method of adding a fluorine-containing surfactant, the surfactant is liable to bleed out due to lack of compatibility, and the surface modification effect is not long-lasting. Also, in the method of adding a random copolymer,
It cannot be said that the affinity with the resin is excellent, and the surface modification effect is not persistent. On the other hand, the method of adding the graft copolymer, the block copolymer, compared to the random copolymer,
Since the compatibility and the affinity are good, the durability of the surface modification effect can be expected to be relatively good. However, although the compatibility and the affinity are improved, a known coating composition for surface hardening is used. Articles (JP-A-53-102936, JP-A-53-40)
79 gazette, the same 53-104638 gazette, the same 54-97633 gazette,
56-861, 56-127635, 56-141309.
However, in the method of simply adding a graft copolymer or a block copolymer to the cured coating, chemical bonding with the cured coating can hardly be expected, and thus there is a problem in permanently maintaining the surface modification effect. Further, a surface-curing coating composition containing a graft copolymer or a block copolymer is said to cause haze (cloudiness) in the coating when the surface of a synthetic resin molded product is coated and cured with active energy rays. There are drawbacks.

[Problems to be Solved by the Present Invention]

The present invention provides a technique for imparting durable water and oil repellency, non-adhesiveness, and stain resistance to a synthetic resin molded article surface at the same time as chemical resistance, scratch resistance, and the like. It is intended to provide a coating composition capable of forming a highly transparent crosslinked cured film with little haze, even though it contains a fluorine-containing block copolymer.

[Means for solving problems]

In view of the circumstances of the above problems, the present inventors have conducted extensive studies, and as a result, use an active energy ray-curable coating composition containing a block copolymer having a specific modification, and produce it as a synthetic resin molded product. The present invention has been completed by finding that the above-mentioned problems can be solved at once by coating the same on the surface of (1) and irradiating it with an active energy ray under specific conditions to form a crosslinked cured coating having a specific thickness range.

That is, the present invention relates to (1) (A) a modified hydrogen-containing fluorine-containing (meth) acrylic acid ester polymer block, and a (meth) acrylic acid ester having active hydrogen and a (meth) acrylic acid ester. Block copolymer consisting of polymer block
100 to 100 parts by weight of (B) polyisocyanate compound 0.1 to 200
A ternary addition product (D) obtained by adding 0.01 part by weight to (C) 0.01 to 150 parts by weight of a compound having at least one active hydrogen and at least one polymerizable double bond is used as an active energy ray-curable positive composition. Coating composition containing 0.1 to 100 parts by weight per 100 parts by weight of the product (E) (2) The block copolymer (A) is a (meth) acrylic acid ester polymer block having a (per) fluoroalkyl group. The coating composition according to claim 1, which is a block copolymer comprising a copolymer block of a (meth) acrylic acid ester having an alcoholic hydroxyl group and a (meth) acrylic acid ester (3) Compound (C) Is a compound having at least one alcoholic hydroxyl group and at least one (meth) acryloyloxy group, and the coating composition according to claim 1 or 2. This coating composition is exposed to active energy rays in the air to give chemical resistance, scratch resistance, abrasion resistance,
It is possible to form a crosslinkable cured film having excellent weather resistance, durability, and water / oil repellency, non-adhesiveness, and stain resistance.

The active energy ray-curable coating composition of the present invention, when the active energy ray-curable compound is crosslinked and cured by irradiation with the active energy ray to form a crosslinked cured film, the modified block copolymer is also chemically crosslinked and cured. As it produces a bond, it has the various excellent coating properties described above and
Surprisingly, it is possible to form a highly transparent cross-linked cured coating with a low haze even though it contains a fluorine-containing block copolymer.

The block copolymer (A) used in the present invention comprises a fluorine-containing (meth) acrylic acid ester polymer block containing no active hydrogen, a (meth) acrylic acid ester having active hydrogen, and a (meth) acrylic acid ester. And a block copolymer of

The fluorine-containing (meth) acrylic acid ester monomer containing no active hydrogen has, for example, a structural formula represented by the following general formulas (I) to (VI).

CH ₂ ═CR ₁ COOR ₂ Rf (I) [wherein, Rf is a perfluoroalkyl group represented by CnF ₂ n ₊₁ , R ₂ is an alkylene group represented by —CmH ₂ m ^— , —CR ₃ H
_{-, - CH 2 CR 3 H-} ( wherein R ₃ represents an alkyl group represented by CpH ₂ p _+1, p is a positive number of 1 to 10), R ₁ represents a hydrogen atom or a methyl group , N is a positive integer of 1 to 16 and m is 1 to
It is a positive integer of 10. ] CH ₂ ＝ CR ₁ COOR ₃ (CF ₃ ) qOR ₃ …… (II) [In the formula, R ₃ is CmH ₂ mClF ₂ l ₊₁ group, or −CmH ₂ mClF ₂ lH group, R
₂ is an alkylene group represented by _{-CpH 2 p-, -CH 2 CH 2} O
-, R ₁ represents a methyl group, or a hydrogen atom, m is of 0 positive integer, l is a positive integer of 0 to 16, p is from 1 to 10 a positive integer, q is from 1 to 10 It is a positive integer. ] _{CH 2 = CR 1 COOR 2 (} CF 3) nH ...... (III) wherein, R ₂ is --Cm ₂ mH ^- alkylene group represented by, -CR
₃ H-, -CH ₂ CR ₂ H- (in the formula, R ₃ represents an alkyl group represented by CpH ₂ p ₊₁ and p is an integer of 1 to 10), R ₁ represents a hydrogen atom or a methyl group. , N is a positive integer from 1 to 16, m is 1
Is a positive integer from -10. ] Wherein, Rf is, CnF ₂ n perfluoroalkyl group represented by _+1, R ₂ is --Cm ₂ mH ^- alkylene group represented by, -CR
₃ H-, -CH ₂ CR ₃ H- (in the formula, R ₃ represents an alkyl group represented by CpH ₂ p ₊₁ and p is a positive integer of 1 to 10), R ₄
Is an alkyl group represented by CqH ₂ q ₊₁ , R ₄ is a hydrogen atom or a methyl group, n is a positive integer of 1 to 16, m is a positive integer of 1 to 10, and q is a positive integer of 1 to 10. Is an integer. ] Wherein, Rf is, CnF ₂ n perfluoroalkyl group represented by _+1, R ₂ is -CmH ₂ m ^- alkylene group represented by, -CR
₃ H-, -CH ₂ CR ₃ H- (in the formula, R ₃ represents an alkyl group represented by CpH ₂ p ₊₁ and p is a positive integer of 1 to 10), R ₄
Is an alkyl group represented by CqH ₂ q ₊₁ , R ₁ is a hydrogen atom or a methyl group, n is a positive integer of 1 to 16 and m is 1 to 10.
Is a positive integer, and q is a positive integer of 1-10. ] CH ₂ = CR ₁ COOR ₂ R ₃ (VI) [wherein R ₁ is a fluorine atom, CHF ₂ group, CH ₂ F group, CF ₃ group, OCO]
CH ₂ F group, or OCOCHF ₂ group, R ₂ is --Cm ₂ mH ^- alkylene group represented _{by, -CR 3 H -, - CH} 2 CRH- ( wherein, R ₃ is CpH ₂ p
Represents an alkyl group represented by ₊₁ and p is a positive integer of 1 to 10. ), R ₃ is an alkyl group represented by CqH ₂ q ₊₁ ,
Or a perfluoroalkyl group represented by CrF ₂ r ₊₁ or-(CF ₂ ) lH, m is a positive integer of 1 to 10, and q is 0.
Is a positive integer of 1 to 10, r is a positive integer of 1 to 16, and l is a positive integer of 1 to 16. ] As a specific example of the general formula (1), CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ OCOCH = CH ₂ CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ OCOCH (CH ₃ ) = CH ₂ CF ₃ CH ₂ OCOCH = CH ₂ and so on.

As a specific example of the general formula (II), CF ₃ CH ₂ OCH ₂ CH ₂ OCOCH = CH ₂ HCF ₂ CF ₂ OCH ₂ CH ₂ OCOCH = CH ₂ C ₂ F ₅ (CH ₂ CH ₂ O) ₂ CH ₃ OCOCH ＝ CH ₂ C ₈ F ₁₇ OCH ₂ CH ₂ OCOC (CH ₃ ) ＝ CH ₂ and so on.

As a specific example of the general formula (III), _{H (CF 2) 8 CH 2} OCOCH = CH 2 H (CF 2) 4 CH 2 OCOCH = CH 2 H (CF 2) 6 CH 2 OCOC (CH 3) = CH 2 CF 3 (CF 2) 8 CFHCF 2 OCOCH = CH ₂ and so on.

As a specific example of the general formula (IV), C ₇ F ₁₅ CON (C ₂ H ₅ ) CH ₂ OCOC (CH ₃ ) = CH ₂ C ₂ F ₅ CON (C ₂ H ₅ ) CH ₂ OCOCH = CH ₂ CF ₃ (CF ₂ ) ₂ CON (CH ₃ ) CH (CH ₃ ) CH ₂ OCOCH = CH ₂ CH ₃ (CF ₂ ) ₇ CON (CH ₂ CH ₂ CH ₃ ) CH ₂ CH ₂ OCOC (CH ₃ ) = CH There are ₂ etc.

As a specific example of the general formula (V), CF ₃ (CF ₂ ) ₇ SO ₂ N (CH ₃ ) CH ₂ CH ₂ OCOC (CH ₃ ) = CH ₂ CF ₃ (CF ₂ ) ₇ SO ₂ N (CH ₃ ) CH ₂ CH ₂ OCOC = CH ₂ C ₈ F ₁₇ SO ₂ N (CH ₃ ) (CH ₂ ) ₁₀ OCOCH = CH ₂ C ₂ F ₅ SO ₂ N (C ₂ H ₅ ) CH ₂ CH ₂ OCOC (CH ₃ ) = CH ₂ C ₈ F ₁₇ SO ₂ N (CH ₃ ) (CH ₂ ) ₄ OCOCH = CH ₂ C ₂ F ₅ SO ₂ N (C ₃ H ₇ ) CH ₂ CH ₂ OCOC (CH ₃ ) = CH ₂ C ₂ F ₅ SO ₂ N (C ₂ H _5), and the like _{C (C 2 H 5) HCH} 2 OCOC = CH 2.

As a specific example of the general formula (VI), CH ₃ OCOCF = CH ₂ , FCH ₂ CH ₂ OCOCF = CH ₂ C ₂ H ₅ OCOC (CH ₂ F) = CH ₂ , CH ₃ CHOC (CHF ₂ ) = CH ₂ , C ₃ H ₇ OCOC (CF ₃ ) = CH ₂ , CH ₃ OCOC (OCOCH ₂ F) = CH ₂ , C ₈ H ₁₇ OCOC (CF ₃ ) = CH ₂ , HC ₃ F ₆ OCOOF = CH ₂ , C ₈ H ₁₇ OCOC (OCOCH ₂ F) = CH ₂ etc.

Among these fluorine-containing (meth) acrylic acid ester monomers which do not contain active hydrogen, the compounds of the structural formulas represented by the general formulas (I) to (III) are particularly preferable because of the good transparency of the crosslinked and cured coating. preferable.

These fluorine-containing (meth) acrylic acid ester monomers containing no active hydrogen are used alone or in combination of two or more, or other than the above in the range where the modification effect of the block copolymer can be exhibited. The vinyl type monomer can be added.

Examples of the (meth) acrylic acid ester monomer having active hydrogen include 2-hydroxyethyl (meth) acrylate, ethylene glycol mono (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2
-Hydroxy 3-methoxypropyl (meth) acrylate, 2-hydroxy 3-butoxypropyl (meth) acrylate, 2-hydroxy 3- (2 ethylhexyloxy) propyl (meth) acrylate, 2-hydroxy 3
Examples thereof include phenyloxypropyl (meth) acrylate.

As the (meth) acrylic acid ester monomer, for example,
Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth)
Acrylate, cyclohexyl (meth) acrylate,
Stearyl (meth) acrylate, lauryl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, Examples thereof include (meth) acrylic acid esters containing no active hydrogen, such as Don and tetrahydrofurfuryl (meth) acrylate.

The method for synthesizing the block copolymer (A) used in the present invention is described in detail in a publicly known document (JP-A-60-221410). For example, a polymer peroxide or a polyazo compound is used. Using the usual bulk polymerization method,
It can be easily obtained by performing the suspension polymerization method, the solution polymerization method and the emulsion polymerization method in two steps. That is, the first
In the step, random copolymerization of (meth) acrylic acid ester and (meth) acrylic acid ester having active hydrogen is carried out to obtain a random copolymer containing a peroxy bond or an azo bond, and in the second step, fluorine-containing compound is further added. A block copolymer (A) obtained by adding a (meth) acrylic acid ester to cleave a peroxy bond or an azo bond in the random copolymer to polymerize a fluorine-containing (meth) acrylic acid ester is obtained.

The polymerization ratio of the fluorine-containing polymer block and the fluorine-free polymer block in the block copolymer (A) was 10/9.
0 to 90/10, more preferably 20/80 to 65/35. When the fluorine-containing polymer block has a ratio of less than 10/90, the water and oil repellency and tack resistance are insufficient, and the ratio of 90/1
If it exceeds 0, it is difficult to form a chemical bond during cross-linking and curing, and the durability is poor. Further, the weight ratio of the (meth) acrylic acid ester having active hydrogen to the (meth) acrylic acid ester in the polymer block containing no fluorine in the block copolymer (A) is 1/99 to 85/15. , And more preferably 5/95 to 5
It is 0/50. When the weight ratio of the (meth) acrylic acid ester having active hydrogen is less than 1/99, the reaction with the polyisocyanate compound in the next step is not sufficiently performed,
Lack of durability. On the other hand, if it exceeds 85/15, the gelled polymer will be generated violently during the reaction with the polyisocyanate compound, making it unusable.

The polyisocyanate compound (B) used in the present invention is 2
A compound having an isocyanate group having a valence of at least 3, such as 2,6-tolylene diisocyanate, diphenylmethane-4,4'-diisocyanate, hexamethylene diisocyanate, tetramethylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, Examples thereof include 1,5-naphthylene diisocyanate, 3,3′-dimethyl-4,4′-biphenylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, and the like, or adduct compounds of these with water, trimethylolpropane, and the like. Of these, the isocyanate compound represented by the following chemical formula, which is a biuret form of hexamethylene diisocyanate Alternatively, a polyisocyanate compound having an isocyanurate ring represented by the following general formula.

(In the formula, R represents a hexamethylene group, a methylcyclohexane group or a toymethylhexamethylene group.) Alternatively, isophorone diisocyanate and lysocyanate are particularly preferable examples. You may use these polyisocyanate compounds in mixture of 2 or more types. Examples of the compound (C) having at least one active hydrogen and at least one polymerizable double bond used in the present invention include 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl ((meth)). Acrylate, 2-hydroxy-3-methoxypropyl (meth) acrylate, 2-hydroxy3
-(2 Ethylhexyloxy) propyl (meth) acrylate, glycerin mono (meth) acrylate, glycerin di (meth) acrylate, trimethylolpropane mono (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol mono (meth) Acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol mono (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra ( Examples thereof include (meth) acrylate and dipentaerythritol penta (meth) acrylate. Among these compounds, it is particularly preferable that the compound having one alcoholic hydroxyl group is the main component. These compounds may use 1 type (s) or 2 or more types.

Examples of the method for synthesizing the ternary addition product (D) used in the present invention include, for example, the block copolymer (A), the polyisocyanate compound (B) and the compound (C) in the presence and / or absence of a solvent. Below, it can be easily synthesized using, for example, didibutyltin dilaurate as a reaction catalyst. An addition amount of dibutyltin dilaurate of 200 ppm is usually sufficient. As the polymerization inhibitor, for example, hydroquinone dimethyl ether may be added at about 50 ppm. Reaction temperature is 60-8
The standard reaction time is about 4 hours at 0 ° C. The reaction is preferably carried out while passing dry air. The reaction may be carried out by simultaneously charging the three components, but first, a predetermined amount of the block copolymer (A) and a large amount of the polyisocyanate compound (B) are reacted, and then the compound (C) is added to substantially add them. React until the isocyanate groups disappear,
It is particularly preferable to synthesize the addition product (D) in order to prevent the formation of a gel-like product.

The weight ratio (B) / (A) of the polyisocyanate compound (B) added to the fluorine-containing block copolymer (A) is 0.1 /
It is 100 to 200/100, preferably 1/100 to 100/100, and more preferably 10/100 to 80/100. (B) / (A) is 0.1 / 100
If the amount is less than the above, the reaction with the polymerizable double bond group-containing compound (C) is not sufficiently performed, and the chemical bond with the crosslinked cured film is insufficient, resulting in poor durability. If (B) / (A) exceeds 200/100, the water / oil repellency becomes insufficient.

Further, the weight ratio (C) / (A) of the polymerizable double bond group-containing compound (C) to be reacted with the fluorine-free block copolymer (A) via the polyisocyanate compound (B) is 0.01 to
100 to 150/100 is preferably 0.1 / 100 to 100/100, and more preferably 1/100 to 70/100. When (C) / (A) is less than 0.01 / 100, the polymerizable double bond group is not sufficiently introduced and the durability is poor. When (C) / (A) exceeds 150/100, the water / oil repellency becomes insufficient.

The active energy ray-curable composition (E) used in the present invention is publicly known (Japanese Patent Laid-Open Nos. 53-102936 and 53-4079).
No. 53, No. 104638, No. 54-97633, No. 5
6-55464, 56-99238, 56-122840, 59-51908, 59-80403, 59-
No. 80410, No. 53-2567, No. 53-552611, No. 59-41366, No. 59-84926, No. 59-86
631, JP 59-8666 JP, JP 59-204624 JP, etc.) active energy ray-curable composition can be used, but above all, detailed description of JP-A-59-51908. The active energy ray-curable composition (E) containing a mixture of the specific polyfunctional urethane (meth) acrylate and the reactive monomer described in 1) as a main organism has good compatibility with the addition product (D). In addition, it is particularly preferable because it forms a film having excellent flexibility.

Further, as preferable examples of the active energy ray-curable composition (E), the composition described in the detailed description of JP-A-56-141309 and the detailed description of JP-A-56-861 are described. The composition of is mentioned.

The addition amount of the addition product is selected from the range of 0.1 to 100 parts by weight, preferably 1 to 50 parts by weight, based on 100 parts by weight of the active energy ray-curable composition. When the addition amount of the addition product (D) is 0.1 part by weight or less, water repellency and oil repellency, stain resistance and the like are insufficient, and when it exceeds 100 parts by weight, the adhesion is deteriorated and the surface hardness is lowered.

The amount of the coating composition applied to the surface of the synthetic resin molded article varies depending on the amount of the monomer mixture contained in the coating composition or the purpose, but the film thickness of the crosslinked cured film is 1 to 30.
It is preferable that the coating is performed in the range of μ, more preferably in the range of 1 to 9 μ. If the film thickness is less than 1 μm, the abrasion resistance is poor, and if it exceeds 30 μm, the cured film is inferior in flexibility, and cracks are likely to occur, which may result in a decrease in strength of the molded product itself. It is not preferable.

As a method of applying the coating composition to the synthetic resin molded article, a method such as brush coating, flow coating, spray coating, spin coating or dip coating is adopted. Since each method has advantages and disadvantages, it is necessary to appropriately select the coating method depending on the intended use. For example, brush coating or flow coating is suitable when you want to improve the surface of only a part of the target synthetic resin molded product, and spray coating when the surface shape of the molded product is complicated, the molded product is flat. When the shape is symmetrical, spin coating is suitable, and when the shape of the molded product is rod or sheet, dip coating is suitable.

In order to crosslink and cure the applied coating, ultraviolet rays emitted from a light source such as a xenon lamp, a low pressure mercury lamp, a high pressure mercury lamp or a long high pressure mercury lamp, or an electron beam extracted from an electron beam accelerator of usually 20 to 2000 KV, α rays, β Rays, active energy rays such as gamma rays may be used. From the viewpoint of practicality or workability, ultraviolet rays are most preferable as the irradiation radiation source. Further, as the light source, the coating composition of the present invention is more excellent in active energy ray curing properties than conventionally known coating compositions, and therefore, it generates ultra-high pressure mercury lamps or high pressure that generate ozone during use and make the environment worse. Even if a mercury lamp is not used, a low-pressure mercury lamp forms a crosslinked cured coating having very excellent coating performance.

The active energy ray irradiation atmosphere may of course be an inert gas atmosphere such as nitrogen gas or carbon dioxide gas or an atmosphere in which the oxygen concentration is lowered, but the coating composition of the present invention is used in a normal air atmosphere. However, it is possible to form a crosslinked cured coating having excellent coating characteristics. The irradiation atmosphere temperature may be room temperature, or may be an atmosphere heated to such an extent that harmful deformation of the base synthetic resin molded article does not occur.

As the additive that can be added to the coating composition of the present invention, known substances can be used as long as the coating film performance can be achieved according to the purpose. For example, when transparency is required, chain transfer agents (eg mercaptans, amines), storage stabilizers (eg diethylhydroxyamine, etc.), stabilizers (eg Light stabilizers, UV stabilizers, phosphorus stabilizers, ionic stabilizers, etc.), plasticizers (eg, epoxy resins, cetyl vinyl ether, etc.) that do not contain reactive double bonds and are homogeneously compatible with the coating composition. Substances that dissolve and give plasticity to the cured coating),
It is possible to use a viscosity super-adjusting substance, an antistatic substance, an antifogging substance and the like.

[Action / effect]

Explaining the action in the coating composition of the present invention,
Its characteristic is that it contains a fluorine-containing block copolymer having a specific modification.

It has been conventionally known that fluorine-containing polymers exhibit functions such as water / oil repellency, non-adhesiveness, corrosion resistance, heat resistance, low friction resistance, and weather resistance. These functions are because the electronegativity of fluorine atoms is extremely high, so that the binding force between fluorine and carbon atoms is strong.

Since the polarizability of fluorine atoms is small, the intermolecular cohesive force between fluorine-containing compounds is small and the surface tension is extremely small.

It comes from the characteristic. Such a function is not possessed by many polymer substances containing a (per) fluoroalkylene group or a (per) fluoroalkyl group, and can be said to be an excellent property unique to a fluorine-containing polymer.

Fluorine-containing polymers have such excellent properties, but not only have poor compatibility with other polymer substances but also poor solubility in low-molecular substances, so that they should be added to coating compositions. Various measures were necessary.

As in the present invention, a block copolymer with a (meth) acrylic acid ester monomer is formed, and the (meth) acrylic acid ester polymer block has a polymerizable double bond in the side chain via a urethane bond or the like. The modified fluorine-containing block copolymer is
Not only the unique properties of the fluorine-containing polymer are imparted, but also the chemical bond is formed at the same time as the curable substance at the time of curing the active energy ray, so that the sustainability of the properties becomes excellent.

In addition, in the case of an active energy ray-curable composition, generally, if the abrasion resistance is increased, the flexibility is lowered or the adhesion is lowered. On the contrary, if the adhesion is improved,
Although abrasion resistance tends to be sacrificed, the coating composition system containing the modified block copolymer of the present invention provides a good balance between abrasion resistance and adhesion.

Furthermore, when an unmodified fluorine-containing block copolymer is added to a known active energy ray-curable composition to form a film, and when crosslinked and cured by active energy rays, haze (cloudiness) occurs during crosslinking and curing. When the fluorine-containing block copolymer is modified by the method of the present invention, surprisingly, a highly transparent crosslinked cured film with very little haze is generated. When the curable composition coating film is crosslinked and cured,
This is probably because the modified fluorine-containing block copolymer produces chemical bonds as a component of the crosslinked cured coating.

〔Example〕

The contents of the present invention will be described in more detail with reference to the following examples. The measurement and evaluation in the examples were carried out by the following methods.

(1) Wear resistance a Falling sand wear 400 g of a silicon carbide abrasive was dropped on a crosslinked hardened film according to the method of JIS T 8147-1975, and the haze value immediately after the test (the haze in JIS K 7105-1981 was used. The wear resistance is represented by the difference.). The smaller the value, the better the wear resistance.

b Tapered wear In accordance with the method of ASTM D-1044, wear wheel CS-10F, load 5
The coated surface is abraded 100 revolutions under the condition of 00 g, and the abrasion resistance is expressed by the difference in haze value (measured according to JIS K 7105) before and after the test. The smaller the value, the better the wear resistance.

(2) Adhesion Adhesion was carried out in accordance with the goggles test in JIS K 5400-1979. Judgment is indicated by how many out of 100 gobangs were in close contact.

(3) Flexibility A crosslinked cured film is formed on the surface of a sheet-shaped synthetic resin molded product having a thickness of 2 to 3 mm, and a test piece with a width of 6 mm and a length of 5 cm is cut out from this, and bending is applied by applying force from both ends. Find the angle from the horizontal when the coating cracks. The larger this angle, the better the flexibility of the coating.

(4) Chemical resistance Various chemicals are dripped on the cross-linked cured film while keeping them horizontal so that 0.5mm does not flow out, and after leaving them for 24 hours at a temperature of 23 ° C and a humidity of 50%, wipe off the chemicals. The appearance was evaluated.

(5) Non-adhesive A cross-linked cured film is formed on the surface of a sheet-shaped molded product, and cellophane tape (Cellotape 18 mm x 35 m manufactured by Nichiban Co., Ltd.) is adhered to the film, and then the peel strength is measured at an angle of 180 degrees. did. The lower the peel strength, the better the non-adhesiveness.

(6) Surface smoothness The surface smoothness was determined according to the 60 degree specular gloss in JIS K-5400-1979.

(7) Water and oil repellency The contact angle with water or decane was measured. (The measurement method is
“Testing method and evaluation of polymeric materials” was performed according to the publication by Baifukan Co., Ltd.) The larger the angle, the better the water repellency or oil repellency.

(8) Contamination resistance Magic ink (black) was applied to the surface of the crosslinked cured coating, and after 100 hours, wiped with xylene to evaluate the appearance.

Judgment criteria ◎ No traces are left at all ○ Some traces are left, but the appearance is not damaged.

△ Traces remain to the extent that the appearance is damaged.

× The mark remains completely.

(9) The weather resistance test piece was put in a Sansaya Inweather meter at 1000 and
After holding for 2000 hours, stain resistance, non-adhesiveness and water / oil repellency were evaluated.

(10) Optical characteristics Light transmittance and haze (cloudiness value) in JIS K 7105-1981
I went according to.

Synthesis of fluorine-containing block copolymer Synthesis example (1) To a reactor equipped with a thermometer, a stirrer, a reflux condenser and a dropping funnel, 150 g of toluene was charged, and heated to 65 ° C while blowing nitrogen gas, 150 g of methyl ethyl ketone, 100 g of toluene, 45 g of methyl acrylate, 140 g of methyl methacrylate, 15 g of 2-hydroxyethyl acrylate
Then, a mixture of 30 g of Polymeric peroxide ^{1) and} 30 g of it was added dropwise over 4 hours, and then a polymerization reaction was further carried out for 3 hours. After the polymerization is complete, cool to room temperature and then use toluene 100
g, 100 g of methyl ethyl ketone and fluorine-containing acrylate
^{2) A} mixture of 70 g was added, and the mixture was heated to 75 ° C. while blowing nitrogen gas, and a polymerization reaction was carried out for 5 hours. After the reaction mixture was cooled, it was poured into a large amount of methanol to separate the fluorine-containing block copolymer (1), and then vacuum dried.

The obtained fluorine-containing block copolymer (1) was dissolved in a mixture of toluene and methyl ethyl ketone (toluene / methyl ethyl ketone = 35/65 weight ratio) so as to be 30% by weight, and the viscosity at 25 ° C. was measured. By the way, 3.0 Poise Atsuta. As a result of elemental analysis, the weight ratio of the fluorine-containing acrylate polymer block was 28 wt%.

1) Polymeric peroxide; 2) Fluorine-containing acrylate; Synthesis Example (2) A fluorine-containing block copolymer (2) was obtained under the same conditions as in Synthesis Example (1) except for the following conditions.

Methyl acrylate 45g, ethyl acrylate 75g, methyl methacrylate 140g, 100g 2-hydroxyethyl acrylate 15g, 25g fluorine-containing acrylate 70g 1
Changed to 80g respectively.

The viscosity of the obtained fluorine-containing block copolymer (2) was 3.3.
It was a poise. As a result of elemental analysis, the weight ratio of the fluorine-containing acrylate polymer block was 46 wt%.

Synthesis Example (3) A fluorine-containing block copolymer (3) was obtained under the same conditions as in Synthesis Example (2) except for the following conditions.

100 g of methyl methacrylate was changed to 75 g, 15 g of 2-hydroxyethyl acrylate was changed to 50 g of 2-hydroxy-3-butoxypropyl acrylate, and fluorine-containing acrylate was changed to fluorine-containing methacrylate ³⁾ .

3) Fluorine-containing methacrylate; The viscosity of the obtained fluorine-containing block copolymer (3) was 3.3.
It was a poise. As a result of elemental analysis, the weight ratio of the fluorine-containing acrylate polymer block was 44 wt%.

Synthesis Example (4) A fluorine-containing block copolymer (4) was obtained under the same conditions as in Synthesis Example (1) except for the following conditions.

Methyl acrylate 45g butyl acrylate 35g Methyl methacrylate 140g 120g 2-Hydroxyethyl acrylate 15g 45g Fluorine-containing acrylate 70g 2
Changed to 55g respectively.

The viscosity of the obtained fluorine-containing block copolymer (4) was 4.0.
It was a poise. As a result of elemental analysis, the weight ratio of the fluorine-containing acrylate polymer block was 57 wt%.

Modification of fluorine-containing block copolymer Variant (1) 400 g of methyl ethyl ketone and 400 ml of fluorine-containing block copolymer synthesized in Synthesis Example (1) in a reactor equipped with a thermometer, a stirrer and a reflux condenser. (1) After charging 100 g to make a uniform solution, 100 g of hexamethylene diisocyanate-made pure body (Diuranate 24A manufactured by Asahi Kasei Kogyo Co., Ltd.) and 200 ppm of dibutyltin dilaurate were charged and uniformly dissolved, and then heated to 70 ° C. And reacted for 4 hours. Next, the reaction solution was cooled to room temperature, 90 g of 2-hydroxyethyl acrylate and 50 ppm of hydroquinone dimethyl ether were added, and the mixture was heated to 65 ° C. while passing dry air and reacted for 4 hours. After cooling to room temperature again, the mixture was poured into a large amount of isopropyl alcohol to separate the modified fluorine-containing block copolymer (1-1) and then vacuum dried.

The obtained modified fluorine-containing block copolymer (1-1) was mixed with toluene and methyl ethyl ketone (35/65 weight ratio).
It was dissolved in 30% by weight and was measured for viscosity at 25 ° C. and found to be 3.2 poise. Further, as a result of analysis by infrared absorption spectrum, it was confirmed that the hydroxyl group disappeared and the polymerizable double bond group was bonded.

Modified Example (2) Modified Example (1) using 100 g of a fluorine-containing block copolymer (2), 130 g of hexamethylene diisocyanate-based vinyl compound and 120 g of 2-hydroxyethylene acrylate.
Under the same conditions as above, a modified fluorine-containing block copolymer (2-2) was obtained. The viscosity of the mixed solution of toluene and methyl ethyl ethyl ketone was 3.4 poise, and it was confirmed by infrared absorption spectrum analysis that the hydroxyl groups had disappeared and that a polymerizable double bond was bonded.

Modified Example (3) Modified fluorine-containing block containing 100 g of fluorine-containing block copolymer (3), 250 g of hexamethylene diisocyanate and 220 g of 2-hydroxyethyl acrylate under the same conditions as in Modified Example (1). A copolymer (3-3) was obtained. Obtained modified fluorine-containing block copolymer (3-3)
The viscosity was 3.5 poise, and the disappearance of hydroxyl groups and the bonding of the polymerizable double bond groups were confirmed.

Modified Example (4) A modified fluorine-containing block containing 100 g of a fluorine-containing block copolymer (4), 130 g of hexamethylene diisocyanate-based vinyl compound and 120 g of 2-hydroxyethyl acrylate under the same conditions as in Modified Example (1). As a result of analysis, a copolymer (4-4) was obtained, and the viscosity was 4.2 poise, the disappearance of hydroxyl groups and the result of a polymerizable double bond group were confirmed.

Examples 1 to 8 Biuret form of hexamethylene diisocyanate (Asahi
100g of diuranate 24A) manufactured by Kasei Kogyo Co., Ltd. and Pentae
Lithritol triacrylate (Shin Nakamura Chemical Co., Ltd.)
Made from NK Ester-TMM-3L (content 55%)) 310g
Add dibutyltin dilaurate 300ppm to the mixture
Urethane polyacryle that reacts at 4 ℃ for 4 hours
I got a card. 70% by weight of this urethane-based polyacrylate
Parts, tetrahydrofurfuryl acrylate 15 parts by weight,
A mixture consisting of 15 parts by weight of trimethylolpropane acrylate.
Benzyl dimethyl ketal (chi
Inga Kyur 651, made by Bagaigie ) Add 2 parts by weight
Then, dilute with toluene to obtain a homogeneous solution with a viscosity of 6 cps (23 ° C).
As a liquid, an active energy ray-curable composition (X) was obtained.
Synthesis examples (1) to (4) -modified examples of this composition (X)
Modified fluorine-containing block copolymerization composed of (1) to (4)
Add bodies (1-1) to (4-4) in the amounts shown in Table-1
Mix well and put this mixture in the dipping cell,
Delaglas A (manufactured by Asahi Kasei Corporation), methacrylic resin transparent
Light sheet) for about 1 minute, then at a speed of 50 mm / sec
Pull it up and dry it in an oven at 80 ℃ for about 5 minutes.
Surface hardening by irradiation with a pressure mercury lamp at a distance of 10 cm for a time of 18 seconds
A methacrylic resin sheet was obtained. Obtained surface-hardened metal oxide
The surface characteristics of the rill resin sheet are shown in Table-1. Comparative example
It can be seen that the durability is excellent by comparison.

Comparative Examples 1 to 5 Active energy ray-curable compositions (X) used in Examples 1 to 8 and fluorine-containing block copolymers synthesized in Synthesis Examples (1) to (4) (used as they were without modification. ) Was used to obtain a surface-hardened acrylic resin sheet under the same conditions as in Examples 1 to 8. However, in Comparative Example 5, no fluorine-containing block copolymer was added. The surface characteristics of the obtained sheet are shown in Table-1.

Examples 9-11 50 parts by weight of dipentaerythritol hexaacrylate,
After adding 2 parts by weight of benzoin ethyl ether to 100 parts by weight of a mixture consisting of 60 parts by weight of tetrahydrofurfuryl acrylate and 90 parts by weight of the urethane-based polyacrylate synthesized in Examples 1 to 8, a mixture of toluene and isopropyl alcohol ( Diluted with 1/1 weight ratio and viscosity 8 cps (23
C.) to obtain an active energy ray-curable composition (Y). To the composition (Y), the modified fluorine-containing block copolymer (2-2) was added in the amounts shown in Tables 2 and 3 and mixed well, and this mixed solution was placed in a dipping cell. A surface-cured methacrylic resin and a sheet were obtained in the same manner as in 1 to 8.

The surface characteristics of the obtained surface-cured methacrylic resin and sheet are shown in Table-2 and Table-3.

Comparative Examples 6 to 8 The same composition as the active energy ray-curable composition (Y) used in Examples 9 to 12 and Comparative Example 6 contained 3% by weight of the unmodified fluorine-containing block copolymer (2). Comparative Example 7 was added, and a surface-cured methacrylic resin sheet was obtained under the same conditions as in Examples 1 to 8 without addition. In Comparative Example 8, the methacrylic resin sheet was used as it was without surface hardening. Their surface properties are shown in Table-2.

Modification (5) Using 100 g of a fluorine-containing block copolymer (2), 130 g of hexamethylene diisocyanate-based vinylate, 1000 g of dipentaerythritol pentaacrylate, and 2000 g of methyl ethyl ketone, a modification containing a modified example (1) was performed. A fluorine block copolymer (2-5) was obtained. The obtained modified fluorine-containing block copolymer (2-5) had a viscosity of 4.1 poise, and as a result of infrared absorption spectrum analysis, disappearance of hydroxyl groups and binding of polymerizable double bond groups were confirmed.

Examples 12-14 2 parts by weight of 1-hydroxycyclohexyl phenyl ketone to 100 parts by weight of a mixture consisting of 20 parts by weight of pentanirythritol tetraacrylate, 50 parts by weight of dipentaerythritol hexaacrylate and 30 parts by weight of tetrahydrofurfuryl acrylate. Then, the mixture was diluted with a mixture of toluene, n-butanol, and methyl isobutyl ketone (1: 1: 1 weight ratio) to prepare a uniform solution (Z) having a viscosity of 6 cps (23 ° C.). To this homogeneous solution (Z), the modified fluorine-containing block copolymer (2-5) was added in the amounts shown in Table 4 and mixed well, to obtain a surface-cured methacrylic resin sheet in the same manner as in Examples 1-8. It was The surface properties of the obtained surface-cured methacrylic resin sheet are shown in Table-4.

Comparative Example 10 A surface-cured methacrylic resin sheet was obtained under the same conditions as in Examples 13 to 15, using the homogeneous solution (Z) used in Examples 13 to 15 and the unmodified fluorine-containing block copolymer (2). . The surface characteristics of the obtained surface-cured methacrylic resin sheet are shown in Table-4.

Example 15 10 parts of dipentaerythritol hexaacrylate, 10 parts of dipentaerythritol pentaacrylate, 4 parts of dipentaerythritol tetraacrylate, 6 parts of ethylcarbitol acrylate, 40 parts of isopropyl alcohol
Part, methyl ethyl ketone 20 parts, silicone surfactant ⁴⁾
Active energy ray curable composition (XY) by adding 4 parts of benzoin ethyl ether to 100 parts by weight of 0.2 parts
Got To this composition (XY), 5 parts by weight of modified fluorine-containing block copolymer (2-2) was added and mixed well, placed in a dipping cell and pulled up to a methacrylic resin plate having a thickness of 4 mm at a speed of 10 mm / sec. A film was formed under the conditions described in 1. above, left for 5 minutes, and then irradiated with a 2 KW low-pressure mercury lamp in the air for 20 seconds from a distance of 10 mm to obtain a surface-cured methacrylic resin plate.
The surface characteristics of this resin plate are shown below.

Falling sand wear 4.3, taper wear 5.2, non-adhesiveness 170g, stain resistance ◎, water repellency 108, oil repellency 77, weather resistance (hereinafter Sunshine weather, after 2000 hours in the meter) stain resistance ◎, non The adhesiveness was 240 g, water repellency 92, and oil repellency 53.

4) Silicone surfactant Example 16 An ester compound (AA) was synthesized according to Reference Example 1 of JP-A-56-141309. 25 of this ester compound (AA)
Parts and dipentaerythritol hexaacrylate 15 parts, dipentaerythritol pentaacrylate 15 parts, dipentaerythritol tetraacrylate 10 parts, tetrahydrofuryl acrylate 35 parts, light stabilizer sebacic acid-bis (2,2,6,6-tetra Methyl-4-bipiperidyl) 1 part,
Octadecyl-3- (3,5-ditersialybutyl-4-
Hydroxyphenyl) propionate 0.2 parts Silicone surfactant (the same as used in Example 15) 0.25
Parts, Bunzoin isopropyl ether 1.5 parts, benzophenone 3 parts, isopropyl alcohol 120 parts, toluene 5
An active energy ray-curable composition (XZ) consisting of 0 parts was obtained. To this composition (XZ), 10 parts by weight of the modified fluorine-containing block copolymer (1-1) was added and mixed well, and a 4 mm-thick methacrylic resin plate was dipped to form a film. After leaving this for 2 minutes, using a low-pressure mercury lamp of 2KW in air,
Both sides of the plate were irradiated twice with UV light for 11 seconds from a distance of 10 cm each. The surface characteristics of the obtained surface-cured methacrylic resin plate are shown below.

Falling sand wear 5.1, Taber wear 6.2, non-adhesive 160g, stain resistance ◎, water repellency 109, oil repellency 79, weather resistance (hereinafter, measured by Sunshine weather, after being kept in the meter for 2000 hours)
The stain resistance was ⊚, the non-adhesiveness was 220 g, the water repellency was 96, and the oil repellency was 53.

Comparative Example 11 Active energy ray-curable composition (XZ) used in Example 16
Example 1 without adding the modified fluorine-containing block copolymer
A surface-cured methacrylic resin plate was obtained under the same conditions as in 16. The surface characteristics of this resin plate are shown below.

Falling sand abrasion 6.4, taper abrasion 7.7, non-stickiness 280g, stain resistance ○, water repellency 106, oil repellency 68, weather resistance (hereinafter Sunshine Inn Weather, in meter, after 2000 hours) stain resistance X, non-stick The property was 420 g, the water repellency was 45 g, and the oil repellency could not be measured.

Example 17 200 g of methyl isobutyl ketone and 25 g of a fluorine-containing block copolymer (2) composed of the synthesis example (2) were charged and well stirred, and then 100 g of hexamethylene diisocyanate biuretate and 200 ppm of dibutyltin dilaurate were added, 65
The mixture was heated to ℃ and reacted for 4 hours. Then, 205 g of pentaerythritol triacrylate (NK Ester-TMM-3L, manufactured by Shin-Nakamura Chemical Co., Ltd.) was gradually added and reacted for 5 hours. 100 parts of this reaction mixture, 20 parts of tetrahydrofuryl acrylate, 10 parts of 2-butoxyethyl acrylate,
An active energy ray-curable composition (YZ) consisting of 100 parts of isobutyl alcohol and 70 parts of toluene was obtained. Using the active energy ray-curable composition (YZ) containing this modified fluorine-containing block copolymer, a surface-cured methacrylic resin plate was obtained under the same conditions as in Example 16. The surface characteristics of this resin plate are shown below. Falling sand wear 4.8, taper wear 5.7, non-stick
180g, stain resistance ◎, water repellency 105, oil repellency 63, weather resistance (measured after 2000 hours in Sunshine Weathermeter) stain resistance ◎, non-adhesive 210g, water repellency 92, oil repellency
It was 57.

Claims (3)

[Claims] 1. A block of (A) a fluorine-containing (meth) acrylic acid ester polymer block containing no active hydrogen, and a copolymer block of a (meth) acrylic acid ester and (meth) acrylic acid ester containing active hydrogen. (B) polyisocyanate compound 0.1-
The ternary addition product (D) obtained by adding 200 parts by weight of (C) 0.01 to 150 parts by weight of a compound having one or more active hydrogens and one or more polymerizable double bonds is treated with an active energy ray curable agent. Coating composition containing 0.1 to 100 parts by weight per 100 parts by weight of composition (E) 2. A block copolymer (A) in which a (meth) acrylic acid ester polymer having a (per) fluoroalkyl group and a (meth) acrylic acid ester having an alcoholic hydroxyl group and a (meth) acrylic acid ester. The coating composition according to claim 1, which is a block copolymer comprising a copolymer block with 3. The coating composition according to claim 1, wherein the compound (C) is a compound having at least one alcoholic hydroxyl group and at least one (meth) acryloyloxy group.