JP5504988B2 - Active energy ray curable compound - Google Patents
Active energy ray curable compound Download PDFInfo
- Publication number
- JP5504988B2 JP5504988B2 JP2010055208A JP2010055208A JP5504988B2 JP 5504988 B2 JP5504988 B2 JP 5504988B2 JP 2010055208 A JP2010055208 A JP 2010055208A JP 2010055208 A JP2010055208 A JP 2010055208A JP 5504988 B2 JP5504988 B2 JP 5504988B2
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- Prior art keywords
- group
- meth
- active energy
- energy ray
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- 239000012965 benzophenone Substances 0.000 description 1
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- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229940043232 butyl acetate Drugs 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- VRNCRGHDRGGBLW-UHFFFAOYSA-N cyclopenta-1,2-diene Chemical compound C1CC=C=C1 VRNCRGHDRGGBLW-UHFFFAOYSA-N 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229940093499 ethyl acetate Drugs 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- 239000003906 humectant Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 1
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 1
- 229940011051 isopropyl acetate Drugs 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 1
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- JESXATFQYMPTNL-UHFFFAOYSA-N mono-hydroxyphenyl-ethylene Natural products OC1=CC=CC=C1C=C JESXATFQYMPTNL-UHFFFAOYSA-N 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- SFLRURCEBYIKSS-UHFFFAOYSA-N n-butyl-2-[[1-(butylamino)-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound CCCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCCC SFLRURCEBYIKSS-UHFFFAOYSA-N 0.000 description 1
- WMRNGPYHLQSTDL-UHFFFAOYSA-N n-cyclohexyl-2-[[1-(cyclohexylamino)-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound C1CCCCC1NC(=O)C(C)(C)N=NC(C)(C)C(=O)NC1CCCCC1 WMRNGPYHLQSTDL-UHFFFAOYSA-N 0.000 description 1
- 150000004780 naphthols Chemical class 0.000 description 1
- 150000004005 nitrosamines Chemical class 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 1
- 125000001484 phenothiazinyl group Chemical class C1(=CC=CC=2SC3=CC=CC=C3NC12)* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000003356 phenylsulfanyl group Chemical group [*]SC1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- DOIRQSBPFJWKBE-UHFFFAOYSA-N phthalic acid di-n-butyl ester Natural products CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- UFUASNAHBMBJIX-UHFFFAOYSA-N propan-1-one Chemical compound CC[C]=O UFUASNAHBMBJIX-UHFFFAOYSA-N 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 229940066767 systemic antihistamines phenothiazine derivative Drugs 0.000 description 1
- UWNNZXDNLPNGQJ-UHFFFAOYSA-N tert-butyl 2-ethylhexanoate Chemical compound CCCCC(CC)C(=O)OC(C)(C)C UWNNZXDNLPNGQJ-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Description
本発明は、活性エネルギー線硬化性化合物に関する。詳しくは、各種基材との密着性に優れ、耐候性及び耐磨耗性に優れる硬化層を形成し得る活性エネルギー線硬化性組成物に好適に使用される活性エネルギー線硬化性化合物に関する。 The present invention relates to an active energy ray-curable compound. Specifically, the present invention relates to an active energy ray-curable compound that is suitably used for an active energy ray-curable composition that can form a cured layer that has excellent adhesion to various base materials and is excellent in weather resistance and abrasion resistance.
太陽光線に含まれる紫外線が、塗膜に含まれる化合物の化学結合を切断して劣化させることはよく知られており、特に屋外のような太陽光線の照射量が多いところで使用される塗膜には高度な耐候性が求められる。 It is well known that the ultraviolet rays contained in the sun rays break and degrade the chemical bonds of the compounds contained in the coating film, especially in coating films used where there is a large amount of sunlight irradiation, such as outdoors. Requires high weather resistance.
従来より、塗料に耐候性を有する添加剤（以下、耐候性添加剤という）を加え、塗膜に求められる耐候性を付与することがなされている。耐候性を有する添加剤としては、たとえば、ベンゾフェノン系、ベンゾトリアゾール系に代表される紫外線吸収剤、ピペリジン系、ヒンダードフェノール等の酸化防止剤、リン、イオウ原子を有する過酸化物分解剤などが挙げられる。 Conventionally, an additive having weather resistance (hereinafter referred to as a weather resistance additive) is added to a paint to impart the required weather resistance to the coating film. Examples of the additive having weather resistance include ultraviolet absorbers typified by benzophenone and benzotriazole, antioxidants such as piperidine and hindered phenol, and peroxide decomposers having phosphorus and sulfur atoms. Can be mentioned.
例えば、特許文献１には、特定の元素を含有する触媒を用い、カルボキシル基とエポキシ基とを反応させて、重合性二重結合を複数有する重合体（Ａ１）を得、該重合体（Ａ１）と重合性単量体（Ａ２）とを含有する感光性樹脂組成物から耐候性に優れる塗膜を形成し得る旨開示されている。そして、耐候性付与向上剤の利用も開示されている。 For example, Patent Document 1 uses a catalyst containing a specific element to react a carboxyl group and an epoxy group to obtain a polymer (A1) having a plurality of polymerizable double bonds, and the polymer (A1 ) And a polymerizable monomer (A2), it is disclosed that a coating film having excellent weather resistance can be formed. And the utilization of a weathering imparting improvement agent is also disclosed.
しかし、これらの耐候性添加剤は低分子量であり、長時間の紫外線暴露によりブリードアウトしてしまい、本来の機能を十分に発揮できない。活性エネルギー線硬化を使用する塗料では、耐候性添加剤に重合性基を付与し、硬化系に組込む工夫がなされたものもあるが、単官能のものが多く、硬化系に十分に組込まれない懸念がある。 However, these weather-resistant additives have a low molecular weight and bleed out due to long-term exposure to ultraviolet rays, so that their original functions cannot be fully exhibited. Some paints that use active energy ray curing have been designed to add a polymerizable group to the weather resistance additive and incorporate it into the curing system, but many are monofunctional and are not fully incorporated into the curing system. There are concerns.
一方で、耐候性骨格を組込んだ高分子化合物が各種市販されているが、重合性基を有していないため、硬度や耐薬品性を落とすなど、別の問題が発生してしまう。 On the other hand, various polymer compounds incorporating a weather-resistant skeleton are commercially available. However, since they do not have a polymerizable group, other problems such as reduction in hardness and chemical resistance occur.
以上の問題を解決するために、耐候性を有する骨格と重合性基の両方を組込んだ高分子化合物が提案されている（特許文献２）。
これにより硬度や耐薬品性などを落とすことなく耐候性を付与することが可能であるが、本発明者らの検討ではそれでも耐候性が不十分であり、耐候性をより最適な形で発揮させる工夫が必要である。
In order to solve the above problems, a polymer compound incorporating both a weather-resistant skeleton and a polymerizable group has been proposed (Patent Document 2).
As a result, it is possible to impart weather resistance without reducing hardness, chemical resistance, etc., but in the study by the present inventors, the weather resistance is still insufficient, and the weather resistance is exhibited in a more optimal form. Ingenuity is necessary.
本発明者らは、上記問題を解決するため、鋭意検討した結果、本発明に達した。
即ち、本発明は、下記アクリル系モノマー（ａ１）〜（ａ４）合計１００重量％中、
ピペリジニル基と（メタ）アクリロイル基とを有するアクリル系モノマー（ａ１）：１０〜８０重量％と、
パーフルオロアルキル基と（メタ）アクリロイル基とを有するアクリル系モノマー（ａ２）：０．１〜２０重量％と、
水酸基と（メタ）アクリロイル基とを有するアクリル系モノマー（ａ３）：１０〜８０重量％と、
必要に応じて（メタ）アクリロイル基を有するその他のアクリル系モノマー（ａ４）：０〜１０重量％とを共重合してなる、水酸基を有するアクリル系プレポリマーと、
イソシアネート基と（メタ）アクリロイル基とを有するアクリル系モノマー（ａ５）との反応生成物であり、
数平均分子量が３０００〜１０００００、
ピペリジニル基の官能基当量が２００〜７０００、
パーフルオロアルキル基の官能基当量が３０００〜２００００、
（メタ）アクリロイル基の官能基当量が２５０〜１６００である、ことを特徴とする、
ピペリジニル基と、パーフルオロアルキル基と、（メタ）アクリロイル基とを有する活性エネルギー線硬化性化合物（Ａ）に関する。
The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems.
That is, the present invention includes the following acrylic monomers (a1) to (a4) in a total of 100% by weight:
Acrylic monomer having a piperidinyl group and a (meth) acryloyl group (a1): 10 to 80% by weight;
Acrylic monomer (a2) having a perfluoroalkyl group and a (meth) acryloyl group: 0.1 to 20% by weight;
Acrylic monomer (a3) having a hydroxyl group and a (meth) acryloyl group: 10 to 80% by weight;
An acrylic prepolymer having a hydroxyl group, copolymerized with other acrylic monomer (a4) having a (meth) acryloyl group, if necessary, from 0 to 10% by weight;
It is a reaction product of an acrylic monomer (a5) having an isocyanate group and a (meth) acryloyl group,
Number average molecular weight is 3000 to 100,000,
The functional group equivalent of the piperidinyl group is 200 to 7000,
The functional group equivalent of the perfluoroalkyl group is 3000-20000,
The functional group equivalent of the (meth) acryloyl group is 250 to 1600,
The present invention relates to an active energy ray-curable compound (A) having a piperidinyl group, a perfluoroalkyl group, and a (meth) acryloyl group.
また、本発明は、下記アクリル系モノマー（ａ１）〜（ａ４）合計１００重量％中、 Further, the present invention provides the following acrylic monomers (a1) to (a4) in a total of 100% by weight,
ピペリジニル基と（メタ）アクリロイル基とを有するアクリル系モノマー（ａ１）：１０〜８０重量％と、Acrylic monomer having a piperidinyl group and a (meth) acryloyl group (a1): 10 to 80% by weight;
パーフルオロアルキル基と（メタ）アクリロイル基とを有するアクリル系モノマー（ａ２）：０．１〜２０重量％と、 Acrylic monomer (a2) having a perfluoroalkyl group and a (meth) acryloyl group: 0.1 to 20% by weight;
水酸基と（メタ）アクリロイル基とを有するアクリル系モノマー（ａ３）：１０〜８０重量％と、 Acrylic monomer (a3) having a hydroxyl group and a (meth) acryloyl group: 10 to 80% by weight;
必要に応じて（メタ）アクリロイル基を有するその他のアクリル系モノマー（ａ４）：０〜１０重量％とを共重合してなる、水酸基を有するアクリル系プレポリマーと、 An acrylic prepolymer having a hydroxyl group, copolymerized with other acrylic monomer (a4) having a (meth) acryloyl group, if necessary, from 0 to 10% by weight;
イソシアネート基と（メタ）アクリロイル基とを有するアクリル系モノマー（ａ５）とを反応させることを特徴とする、 Characterized by reacting an acrylic monomer (a5) having an isocyanate group and a (meth) acryloyl group,
数平均分子量が３０００〜１０００００、 Number average molecular weight is 3000 to 100,000,
ピペリジニル基の官能基当量が２００〜７０００、 The functional group equivalent of the piperidinyl group is 200 to 7000,
パーフルオロアルキル基の官能基当量が３０００〜２００００、 The functional group equivalent of the perfluoroalkyl group is 3000-20000,
（メタ）アクリロイル基の官能基当量が２５０〜１６００である、 The functional group equivalent of the (meth) acryloyl group is 250-1600,
ピペリジニル基と、パーフルオロアルキル基と、（メタ）アクリロイル基とを有する活性エネルギー線硬化性化合物（Ａ）の製造方法に関する。 The present invention relates to a method for producing an active energy ray-curable compound (A) having a piperidinyl group, a perfluoroalkyl group, and a (meth) acryloyl group.
本発明の活性エネルギー線硬化性化合物（Ａ）を含有する活性エネルギー線硬化性組成物は、各種部材との密着性に優れ、耐候性及び耐磨耗性に優れる硬化塗膜を形成し得る。 The active energy ray-curable composition containing the active energy ray-curable compound (A) of the present invention is excellent in adhesion to various members, and can form a cured coating film having excellent weather resistance and abrasion resistance.
本発明の活性エネルギー線硬化性化合物（Ａ）について説明する。
活性エネルギー線硬化性化合物（Ａ）は、ピペリジニル基と、フッ素原子を含有する官能基と、（メタ）アクリロイル基とを有する。
The active energy ray-curable compound (A) of the present invention will be described.
The active energy ray-curable compound (A) has a piperidinyl group, a functional group containing a fluorine atom, and a (meth) acryloyl group.
前記活性エネルギー線硬化性化合物（Ａ）は、例えば以下のようにして得ることができる。
即ち、ピペリジニル基と（メタ）アクリロイル基とを有するアクリル系モノマー（ａ１）と、フッ素原子含有官能基と（メタ）アクリロイル基とを有するアクリル系モノマー（ａ２）と、水酸基と（メタ）アクリロイル基とを有するアクリル系モノマー（ａ３）と、必要に応じて（メタ）アクリロイル基とを有するその他のアクリル系モノマー（ａ４）とを共重合し、水酸基を有するアクリル系プレポリマーを得、イソシアネート基と（メタ）アクリロイル基とを有するアクリル系モノマー（ａ５）中のイソシアネート基を、前記水酸基を有するアクリル系プレポリマー中の水酸基と反応させて得ることができる。
The active energy ray-curable compound (A) can be obtained, for example, as follows.
That is, an acrylic monomer (a1) having a piperidinyl group and a (meth) acryloyl group, an acrylic monomer (a2) having a fluorine atom-containing functional group and a (meth) acryloyl group, a hydroxyl group and a (meth) acryloyl group And an acrylic monomer (a4) having a (meth) acryloyl group, if necessary, to obtain an acrylic prepolymer having a hydroxyl group, It can be obtained by reacting the isocyanate group in the acrylic monomer (a5) having a (meth) acryloyl group with the hydroxyl group in the acrylic prepolymer having a hydroxyl group.
＜ピペリジニル基と（メタ）アクリロイル基とを有するアクリル系モノマー（ａ１）＞
ピペリジニル基を有するアクリル系モノマー（ａ１）は、硬化塗膜に耐候性を付与する機能を担う。
硬化塗膜が紫外線に曝されると、化学結合が切断されラジカルが生成する。生成したラジカルは、硬化塗膜中の化学結合の切断を促進する。活性エネルギー線硬化性化合物（Ａ）に導入されたピペリジニル基は、前記ラジカルと反応し前記ラジカルを不活性化させ、硬化塗膜中の化学結合の切断を抑制する機能を担う。
ピペリジニル基と（メタ）アクリロイル基とを有するアクリル系モノマー（ａ１）としては、４−（メタ）アクリロイルオキシ−２，２，６，６−テトラメチルピペリジン、４−（メタ）アクリロイルオキシ−１，２，２，６，６−ペンタメチルピペリジンなどが挙げられる。
なお、本発明において、(メタ)アクリロイル基とは、アクリロイル基ないしメタクリロイル基の意であり、（メタ）アクリロイルオキシとは、アクリロイルオキシないしメタクリロイルオキシの意である。アクリル系モノマー（ａ２）〜（ａ５）や活性エネルギー線硬化性化合物（Ｂ）〜（Ｃ）の説明においても同様である。
<Acrylic monomer (a1) having piperidinyl group and (meth) acryloyl group>
The acrylic monomer (a1) having a piperidinyl group has a function of imparting weather resistance to the cured coating film.
When the cured coating film is exposed to ultraviolet rays, chemical bonds are broken and radicals are generated. The generated radicals promote the breaking of chemical bonds in the cured coating film. The piperidinyl group introduced into the active energy ray-curable compound (A) has a function of reacting with the radical to inactivate the radical and suppressing the breakage of chemical bonds in the cured coating film.
Examples of the acrylic monomer (a1) having a piperidinyl group and a (meth) acryloyl group include 4- (meth) acryloyloxy-2,2,6,6-tetramethylpiperidine, 4- (meth) acryloyloxy-1, 2,2,6,6-pentamethylpiperidine and the like can be mentioned.
In the present invention, (meth) acryloyl group means acryloyl group or methacryloyl group, and (meth) acryloyloxy means acryloyloxy or methacryloyloxy. The same applies to the description of the acrylic monomers (a2) to (a5) and the active energy ray-curable compounds (B) to (C).
＜フッ素原子含有官能基と（メタ）アクリロイル基とを有するアクリル系モノマー（ａ２）＞
フッ素原子含有官能基を有するアクリル系モノマー（ａ２）は、硬化塗膜に耐候性を付与する機能を担う。その理由としては以下の２つであると考えられる。
（１）Ｃ−Ｈ結合よりも結合が強い（＝結合エネルギーが大きい）Ｃ−Ｆ結合を組込むことで結合が切断されにくくなる。
（２）塗膜が硬化する際、活性エネルギー線硬化性化合物（Ａ）中のフッ素原子含有官能基は表面に配向し易い。そして、これら官能基が表面に配向する際、活性エネルギー線硬化性化合物（Ａ）を構成する前記アクリル系モノマー（ａ１）由来のピペリジニル基も塗膜表面近傍に集中し易くなり、その結果、塗膜内部の劣化を防ぐ。
<Acrylic monomer (a2) having fluorine atom-containing functional group and (meth) acryloyl group>
The acrylic monomer (a2) having a fluorine atom-containing functional group has a function of imparting weather resistance to the cured coating film. There are two reasons for this.
(1) By incorporating a C—F bond having a stronger bond (= higher bond energy) than a C—H bond, the bond is less likely to be broken.
(2) When the coating film is cured, the fluorine atom-containing functional group in the active energy ray-curable compound (A) is easily oriented on the surface. When these functional groups are oriented on the surface, the piperidinyl groups derived from the acrylic monomer (a1) constituting the active energy ray-curable compound (A) are also easily concentrated in the vicinity of the coating film surface. Prevents deterioration inside the membrane.
フッ素原子を有する官能基は、たとえば、２，２，２−トリフルオロエチル基、２，２，３，３，３−ペンタフルオロプロピル基、３，３，４，４，５，５，６，６，７，７，８，８，９，９，１０，１０，１０−ヘプタデカフルオロデシル基、ペンタフルオロフェニル基等のフッ素置換されたアルキル基、アリール基、アラルキル基、などが挙げられ、パーフルオロアルキル基が好ましい。 Examples of the functional group having a fluorine atom include 2,2,2-trifluoroethyl group, 2,2,3,3,3-pentafluoropropyl group, 3,3,4,4,5,5,6, 6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl group, fluorine-substituted alkyl group such as pentafluorophenyl group, aryl group, aralkyl group, etc. A perfluoroalkyl group is preferred.
これら官能基と（メタ）アクリロイル基とを有するアクリル系モノマー（ａ２）としては、たとえば、２，２，２−トリフルオロエチル（メタ）アクリレート、２，２，３，３，３−ペンタフルオロプロピル（メタ）アクリレート、２−（パーフルオロブチル）エチル（メタ）アクリレート、３−（パーフルオロブチル）−２−ヒドロキシプロピル（メタ）アクリレート、２−（パーフルオロヘキシル）エチル（メタ）アクリレート、３−（パーフルオロヘキシル）−２−ヒドロキシプロピル（メタ）アクリレート、２−（パーフルオロオクチル）エチル（メタ）アクリレート、３−（パーフルオロオクチル）−２−ヒドロキシプロピル（メタ）アクリレート、２−（パーフルオロデシル）エチル（メタ）アクリレート、２−（パーフルオロ−３−メチルブチル）エチル（メタ）アクリレート、３−（パーフルオロ−３−メチルブチル）−２−ヒドロキシプロピル（メタ）アクリレート、２−（パーフルオロ−５−メチルヘキシル）エチル（メタ）アクリレート、３−（パーフルオロ−５−メチルヘキシル）−２−ヒドロキシプロピル（メタ）アクリレート、２−（パーフルオロ−７−メチルオクチル）エチル（メタ）アクリレート、３−（パーフルオロ−７−メチルオクチル）−２−ヒドロキシプロピル（メタ）アクリレート、１Ｈ，１Ｈ，３Ｈ−テトラフルオロプロピル（メタ）アクリレート、１Ｈ，１Ｈ，５Ｈ−オクタフルオロペンチル（メタ）アクリレート、１Ｈ，１Ｈ，７Ｈ−ドデカフルオロヘプチル（メタ）アクリレート、１Ｈ，１Ｈ，９Ｈ−ヘキサデカフルオロノニル（メタ）アクリレート、１Ｈ−１−（トリフルオロメチル）トリフルオロエチル（メタ）アクリレート、１Ｈ，１Ｈ，３Ｈ−ヘキサフルオロブチル（メタ）アクリレート等が挙げられる。
なお、フッ素原子含有官能基を有するものが水酸基を有する場合には、後述する水酸基と（メタ）アクリロイル基とを有するアクリル系モノマー（ａ３）には分類せずに、その他のアクリル系モノマー（ａ２）に分類することとする。
Examples of the acrylic monomer (a2) having these functional groups and (meth) acryloyl groups include 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3,3-pentafluoropropyl. (Meth) acrylate, 2- (perfluorobutyl) ethyl (meth) acrylate, 3- (perfluorobutyl) -2-hydroxypropyl (meth) acrylate, 2- (perfluorohexyl) ethyl (meth) acrylate, 3- (Perfluorohexyl) -2-hydroxypropyl (meth) acrylate, 2- (perfluorooctyl) ethyl (meth) acrylate, 3- (perfluorooctyl) -2-hydroxypropyl (meth) acrylate, 2- (perfluoro Decyl) ethyl (meth) acrylate, 2- (perfluoro 3-methylbutyl) ethyl (meth) acrylate, 3- (perfluoro-3-methylbutyl) -2-hydroxypropyl (meth) acrylate, 2- (perfluoro-5-methylhexyl) ethyl (meth) acrylate, 3- ( Perfluoro-5-methylhexyl) -2-hydroxypropyl (meth) acrylate, 2- (perfluoro-7-methyloctyl) ethyl (meth) acrylate, 3- (perfluoro-7-methyloctyl) -2-hydroxy Propyl (meth) acrylate, 1H, 1H, 3H-tetrafluoropropyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate, 1H, 1H, 7H-dodecafluoroheptyl (meth) acrylate, 1H, 1H, 9H-Hexadecafluorononi (Meth) acrylate, IH-1-(trifluoromethyl) trifluoroethyl (meth) acrylate, 1H, 1H, 3H- hexafluoro-butyl (meth) acrylate.
In addition, when what has a fluorine atom containing functional group has a hydroxyl group, it does not classify | categorize into the acrylic monomer (a3) which has the hydroxyl group and (meth) acryloyl group which are mentioned later, Other acrylic monomers (a2 ).
水酸基と（メタ）アクリロイル基とを有するアクリル系モノマー（ａ３）は、後述するイソシアネート基と（メタ）アクリロイル基とを有するアクリル系モノマー（ａ５）との反応点として機能する水酸基を、プレポリマーに導入する機能を担う。
水酸基と（メタ）アクリロイル基とを有するアクリル系モノマー（ａ３）としては、ヒドロキシエチル（メタ）アクリレート、ヒドロキシプロピル（メタ）アクリレート、ヒドロキシブチル（メタ）アクリレート、シクロヘキサンジメタノールモノ（メタ）アクリレート、２，３−ジヒドロキシプロピル（メタ）アクリレート（ヒドロキシ基二官能）、２−ヒドロキシ−３−フェノキシプロピル（メタ）アクリレート、Ｎ−メチロール（メタ）アクリルアミド、ヒドロキシスチレン、ヒドロキノンモノ（メタ）アクリレート、ヒドロキシアルキルビニルエーテル、および、これらをエチレンオキシド変性（ＥＯ変性）、プロピレンオキシド変性（ＰＯ変性）、カプロラクトン変性（ＣＬ変性）等の単官能（メタ）アクリレート、３−（メタ）アクリロイルオキシ−２−ヒドロキシプロピル（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、イソシアヌル酸ＥＯ変性ジ（メタ）アクリレート等の多官能（メタ）アクリレート等が挙げられる。
The acrylic monomer (a3) having a hydroxyl group and a (meth) acryloyl group has a hydroxyl group that functions as a reaction point between an acrylic monomer (a5) having an isocyanate group and a (meth) acryloyl group described later as a prepolymer. Responsible for the functions to be introduced.
Examples of the acrylic monomer (a3) having a hydroxyl group and a (meth) acryloyl group include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate, 2 , 3-Dihydroxypropyl (meth) acrylate (hydroxy functional bifunctional), 2-hydroxy-3-phenoxypropyl (meth) acrylate, N-methylol (meth) acrylamide, hydroxystyrene, hydroquinone mono (meth) acrylate, hydroxyalkyl vinyl ether And monofunctional (meth) acrylates such as ethylene oxide modified (EO modified), propylene oxide modified (PO modified), caprolactone modified (CL modified), 3- (meth) Examples include polyfunctional (meth) acrylates such as acryloyloxy-2-hydroxypropyl (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and isocyanuric acid EO-modified di (meth) acrylate. It is done.
本発明の活性エネルギー線硬化性化合物（Ａ）を得る際には、前記のアクリル系モノマー（ａ１）〜（ａ３）以外に、（メタ）アクリロイル基を有するその他のアクリル系モノマー（ａ４）を用いることができる。
その他のアクリル系モノマー（ａ４）としては、上記記載の水酸基と（メタ）アクリロイル基を有する化合物（ａ３）と異なる化合物、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ブチル（メタ）アクリレート、ヘキシル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、ラウリル（メタ）アクリレート、ステアリル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、ベンジル（メタ）アクリレート、イソボルニル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、２−メトキシエチル（メタ）アクリレート、ポリエチレングリコールアルキルエーテル（メタ）アクリレート、ポリプロピレングリコールアルキルエーテル（メタ）アクリレート、テトラヒドロフルフリル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、Ｎ，Ｎ−ジメチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ−ジエチルアミノエチル（メタ）アクリレート、スチレン、メチルスチレン、などが挙げられる。
In obtaining the active energy ray-curable compound (A) of the present invention, other acrylic monomers (a4) having a (meth) acryloyl group are used in addition to the acrylic monomers (a1) to (a3). be able to.
Other acrylic monomers (a4) include compounds different from the above-described compound (a3) having a hydroxyl group and a (meth) acryloyl group, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl (Meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) Acrylate, 2-methoxyethyl (meth) acrylate, polyethylene glycol alkyl ether (meth) acrylate, polypropylene glycol alkyl ether (meth) acrylate, tetrahydrofurfuryl (meth) ) Acrylate, phenoxyethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, styrene, methyl styrene, and the like.
本発明に用いられる、水酸基を有するアクリル系プレポリマーは次の手順により得られる。
すなわち、ピペリジニル基を有するアクリル系モノマー（ａ１）と、フッ素原子含有官能基を有するアクリル系モノマー（ａ２）と、水酸基を有するアクリル系モノマー（ａ３）と、必要に応じてその他のアクリル系モノマー（ａ４）とをラジカル共重合する。
前記アクリル系モノマー（ａ１）〜（ａ４）の合計１００重量％中、ピペリジニル基を有するアクリル系モノマー（ａ１）：１０〜８０重量％、フッ素原子含有官能基を有するアクリル系モノマー（ａ２）：０．１〜２０重量％、水酸基を有するアクリル系モノマー（ａ３）：１０〜８０重量％、その他のアクリル系モノマー（ａ４）：０〜１０重量％であることが好ましく、（ａ１）：２０〜７０重量％、（ａ２）：１〜１５重量％、（ａ３）：２０〜７０重量％、その他のアクリル系モノマー（ａ４）：０〜５重量％であることがさらに好ましい。
The acrylic prepolymer having a hydroxyl group used in the present invention is obtained by the following procedure.
That is, an acrylic monomer (a1) having a piperidinyl group, an acrylic monomer (a2) having a fluorine atom-containing functional group, an acrylic monomer (a3) having a hydroxyl group, and other acrylic monomers (if necessary) a4) is radically copolymerized.
Acrylic monomer having a piperidinyl group (a1): 10 to 80% by weight, acrylic monomer having a fluorine atom-containing functional group (a2): 0 in a total of 100% by weight of the acrylic monomers (a1) to (a4) 0.1 to 20% by weight, hydroxyl group-containing acrylic monomer (a3): 10 to 80% by weight, other acrylic monomer (a4): preferably 0 to 10% by weight, (a1): 20 to 70% It is more preferable that the weight%, (a2): 1 to 15% by weight, (a3): 20 to 70% by weight, and other acrylic monomer (a4): 0 to 5% by weight.
ピペリジニル基を有するアクリル系モノマー（ａ１）の共重合比が８０重量％を超えると、相対的に水酸基を有するアクリル系モノマー（ａ３）の共重合比率が少なくなる。その結果、次工程でイソシアネート基を有するアクリル系モノマー（ａ５）と反応させるべき水酸基が少なくなり、得られる活性エネルギー線硬化性化合物（Ａ）の（メタ）アクリロイル基当量が大きくなり、形成される硬化塗膜の耐磨耗性が低下する。一方、ピペリジニル基を有するアクリル系モノマー（ａ１）の共重合比が１０重量％未満では、得られる活性エネルギー線硬化性化合物（Ａ）中のピペリジニル基の量が少なくなり、活性エネルギー線硬化性組成物に大量に配合しないと、優れた耐候性を発現することができない。 When the copolymerization ratio of the acrylic monomer (a1) having a piperidinyl group exceeds 80% by weight, the copolymerization ratio of the acrylic monomer (a3) having a hydroxyl group becomes relatively small. As a result, the hydroxyl group to be reacted with the acrylic monomer (a5) having an isocyanate group in the next step is reduced, and the (meth) acryloyl group equivalent of the obtained active energy ray-curable compound (A) is increased and formed. Abrasion resistance of the cured coating is reduced. On the other hand, when the copolymerization ratio of the acrylic monomer (a1) having a piperidinyl group is less than 10% by weight, the amount of the piperidinyl group in the obtained active energy ray-curable compound (A) is reduced, and the active energy ray-curable composition is obtained. Unless it is blended in a large amount with a product, excellent weather resistance cannot be expressed.
フッ素原子含有官能基を有するアクリル系モノマー（ａ２）の共重合比が２０重量％を超えるとフッ素原子の塗膜表面への配向が多くなり、硬化塗膜に撥水・撥油性、滑性、耐候性が付与される反面、硬化塗膜の表面硬度が低下してしまう。一方、フッ素原子含有官能基を有するアクリル系モノマー（ａ２）の共重合比が０．１重量％未満の場合、塗膜表面へのフッ素原子の配向が少なく、さらにピペリジニル基の塗膜表面への配向が少なく、優れた耐候性を発現する事ができない。 When the copolymerization ratio of the acrylic monomer (a2) having a fluorine atom-containing functional group exceeds 20% by weight, the orientation of fluorine atoms on the coating film surface increases, and the cured coating film has water / oil repellency, lubricity, While weather resistance is imparted, the surface hardness of the cured coating film decreases. On the other hand, when the copolymerization ratio of the acrylic monomer (a2) having a fluorine atom-containing functional group is less than 0.1% by weight, the orientation of fluorine atoms on the coating film surface is small, and the piperidinyl group is applied to the coating film surface. The orientation is small and excellent weather resistance cannot be expressed.
水酸基を有するアクリル系モノマー（ａ３）の共重合比が８０重量％を超えると、逆にピペリジニル基を有するアクリル系モノマー（ａ１）の共重合比が少なくなり、耐候性の向上が期待できない。一方、水酸基を有するアクリル系モノマー（ａ３）の共重合比が１０重量％未満だと、前記同様に活性エネルギー線硬化性化合物（Ａ）の（メタ）アクリロイル基当量が大きくなり、形成される硬化塗膜の耐磨耗性が低下する。 If the copolymerization ratio of the acrylic monomer (a3) having a hydroxyl group exceeds 80% by weight, the copolymerization ratio of the acrylic monomer (a1) having a piperidinyl group is conversely reduced, and improvement in weather resistance cannot be expected. On the other hand, when the copolymerization ratio of the acrylic monomer (a3) having a hydroxyl group is less than 10% by weight, the (meth) acryloyl group equivalent of the active energy ray-curable compound (A) is increased as described above, and thus formed curing Abrasion resistance of the coating film decreases.
ラジカル重合時に使用する重合開始剤は溶剤やモノマーに対する溶解性、重合温度、目的とする分子量等に合わせて適当なものを選んで使用できる。たとえば、２，２’−アゾビス（イソブチロニトリル）、２，２’−アゾビス（４−メトキシ−２，４−ジメチルバレロニトリル）、２，２’−アゾビス（２，４−ジメチルバレロニトリル）、２，２−アゾビス（２−メチルプロピオン酸）ジメチル、２，２’−アゾビス（２−メチルブチロニトリル）、１，１’−アゾビス（シクロヘキサン−１−カルボニトリル）、２，２’−アゾビス［Ｎ−（２−プロペニル）−２−メチルプロピオンアミド］、１−［（１−シアノ−１−メチルエチル）アゾ］ホルムアミド、２，２’−アゾビス（Ｎ−ブチル−２−メチルプロピオンアミド）、２，２’−アゾビス（Ｎ−シクロヘキシル−２−メチルプロピオンアミド）、などのアゾ系開始剤、ポリジメチルシロキサンまたはポリエチレングリコール鎖を有するマクロアゾ開始剤、過酸化ジイソブチル、過酸化ジ−ｔ−ブチル、過酸化ベンゾイル、２−エチルヘキサン酸ｔ−ブチル、１，１−ジ−ｔ−ブチルペルオキシ−２−メチルシクロヘキサン等の過酸化物などが挙げられる。 As the polymerization initiator used at the time of radical polymerization, an appropriate one can be selected and used in accordance with solubility in a solvent or monomer, polymerization temperature, target molecular weight and the like. For example, 2,2′-azobis (isobutyronitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile) 2,2-azobis (2-methylpropionic acid) dimethyl, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′- Azobis [N- (2-propenyl) -2-methylpropionamide], 1-[(1-cyano-1-methylethyl) azo] formamide, 2,2′-azobis (N-butyl-2-methylpropionamide) ), 2,2′-azobis (N-cyclohexyl-2-methylpropionamide), azo initiators such as polydimethylsiloxane or polyethylene glycol Peroxides such as diazobutyl peroxide, di-t-butyl peroxide, benzoyl peroxide, t-butyl 2-ethylhexanoate, 1,1-di-t-butylperoxy-2-methylcyclohexane Such as things.
重合開始剤は、プレポリマー重合時のモノマー１００重量部［すなわち、ピペリジニル基を有するアクリル系モノマー（ａ１）と、フッ素原子含有官能基を有するアクリル系モノマー（ａ２）と、水酸基を有するアクリル系モノマー（ａ３）と、必要に応じてその他のアクリル系モノマー（ａ４）との合計１００重量部］に対して、０．１〜１０重量部であることが好ましい。
重合開始剤が０．１重量部未満であると、得られるプレポリマー及び活性エネルギー線硬化性化合物（Ａ）の分子量が大きくなり、活性エネルギー線硬化性化合物（Ａ）を含有する活性エネルギー線硬化性組成合物の粘度が高くなり過ぎるため、塗料として使用する際、塗工適性が低下するおそれがある。
また、重合開始剤が１０重量部よりも多いと、得られるプレポリマーの分子量が小さくなってしまい、プレポリマー中に含まれる水酸基を有しない成分の割合が多くなる。その結果、そのようなプレポリマーと、後述するイソシアネート基を有するアクリル系モノマー（ａ５）とを反応させても反応生成物である活性エネルギー線硬化性化合物（Ａ）中に含まれる(メタ)アクリロイル基を有しない成分の含有量が多くなり、活性エネルギー線硬化性組成物の硬化性が悪化し、硬化塗膜の硬度等が低下してしまうため、好ましくない。同様の理由で、プレポリマーの数平均分子量は３，０００〜１００，０００が好ましい。
The polymerization initiator was 100 parts by weight of monomer during prepolymer polymerization [that is, an acrylic monomer (a1) having a piperidinyl group, an acrylic monomer (a2) having a fluorine atom-containing functional group, and an acrylic monomer having a hydroxyl group. It is preferable that it is 0.1-10 weight part with respect to (a3) and a total of 100 weight part of another acrylic monomer (a4) as needed.
When the polymerization initiator is less than 0.1 part by weight, the molecular weight of the resulting prepolymer and the active energy ray-curable compound (A) increases, and active energy ray curing containing the active energy ray-curable compound (A). Since the viscosity of the adhesive composition is too high, the coating suitability may be reduced when used as a paint.
Moreover, when there are more polymerization initiators than 10 weight part, the molecular weight of the prepolymer obtained will become small and the ratio of the component which does not have a hydroxyl group contained in a prepolymer will increase. As a result, (meth) acryloyl contained in the active energy ray-curable compound (A) which is a reaction product even when such a prepolymer is reacted with an acrylic monomer (a5) having an isocyanate group described later. This is not preferable because the content of the component having no group increases, the curability of the active energy ray-curable composition deteriorates, and the hardness of the cured coating film decreases. For the same reason, the number average molecular weight of the prepolymer is preferably 3,000 to 100,000.
ラジカル重合は無溶剤で行っても、溶剤中で行っても構わない。使用できる溶剤は、たとえば、トルエン、キシレン、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン、イソホロン、酢酸メチル、酢酸エチル、酢酸プロピル、酢酸イソプロピル、酢酸ブチル、酢酸イソブチル、酢酸シクロヘキシル、テトラヒドロフラン、１，４−ジオキサン、プロピレングリコールモノメチルエーテルアセテート、ジエチレングリコールモノエチルエーテルアセテート、メタノール、エタノール、１−プロパノール、２−プロパノール、ブタノール、ダイアセトンアルコール、等が挙げられる。 The radical polymerization may be performed without a solvent or in a solvent. Solvents that can be used are, for example, toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, isophorone, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, cyclohexyl acetate, tetrahydrofuran, 1,4- Examples include dioxane, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, methanol, ethanol, 1-propanol, 2-propanol, butanol, diacetone alcohol, and the like.
ラジカル重合時の温度は、溶剤の沸点や開始剤の組合せによって制限される場合もあるが、通常４０〜１５０℃、好ましくは６０〜１００℃で行われる。 Although the temperature at the time of radical polymerization may be restrict | limited by the combination of the boiling point of a solvent and an initiator, it is 40-150 degreeC normally, Preferably it is carried out at 60-100 degreeC.
活性エネルギー線硬化性化合物（Ａ）の形成に用いられる水酸基を有するプレポリマーの水酸基価は、３０〜３００（ｍｇＫＯＨ／ｇ）であることが好ましく、７０〜２７０（ｍｇＫＯＨ／ｇ）であることがより好ましい。水酸基価が小さすぎると、次工程で導入できる（メタ）アクリロイル基が少なくなり、得られる活性エネルギー線硬化性化合物（Ａ）の（メタ）アクリロイル基当量が大きくなり、形成される硬化塗膜の耐磨耗性が低下する。一方、水酸基価が大きすぎると、ピペリジニル基を有するアクリル系モノマー（ａ１）の共重合比が少なくなり、耐候性の向上が期待できない。 The hydroxyl value of the prepolymer having a hydroxyl group used to form the active energy ray-curable compound (A) is preferably 30 to 300 (mgKOH / g), and preferably 70 to 270 (mgKOH / g). More preferred. If the hydroxyl value is too small, the number of (meth) acryloyl groups that can be introduced in the next step decreases, the (meth) acryloyl group equivalent of the resulting active energy ray-curable compound (A) increases, and the cured coating film formed Abrasion resistance is reduced. On the other hand, if the hydroxyl value is too large, the copolymerization ratio of the acrylic monomer (a1) having a piperidinyl group decreases, and improvement in weather resistance cannot be expected.
本発明の活性エネルギー線硬化性化合物（Ａ）は、前記アクリル系モノマー（ａ１）〜（ａ４）から形成された水酸基を有するアクリル系プレポリマーと、イソシアネート基を有するアクリル系モノマー（ａ５）とを反応させることによって得られる。 The active energy ray-curable compound (A) of the present invention comprises an acrylic prepolymer having a hydroxyl group formed from the acrylic monomers (a1) to (a4) and an acrylic monomer (a5) having an isocyanate group. It is obtained by reacting.
イソシアネート基と（メタ）アクリロイル基とを有するアクリル系モノマー（ａ５）としては、２−（メタ）アクリロイルオキシエチルイソシアネート、２−（２−（メタ）アクリロイルオキシエチルオキシ）エチルイソシアネート等の単官能（メタ）アクリレート、１，１−ビス（（メタ）アクリロイルオキシメチル）エチルイソシアネート等の多官能（メタ）アクリレート等が挙げられる。 Examples of the acrylic monomer (a5) having an isocyanate group and a (meth) acryloyl group include monofunctional groups such as 2- (meth) acryloyloxyethyl isocyanate and 2- (2- (meth) acryloyloxyethyloxy) ethyl isocyanate ( Examples thereof include polyfunctional (meth) acrylates such as (meth) acrylate and 1,1-bis ((meth) acryloyloxymethyl) ethyl isocyanate.
この際の反応条件は水酸基とイソシアネート基の組合せによって適した条件を選ぶ必要があるが、それぞれの持つ二重結合が反応しないよう、反応温度２０〜１１０℃、好ましくは５０〜１００℃で行うことが望ましい。 In this case, it is necessary to select a suitable reaction condition depending on the combination of the hydroxyl group and the isocyanate group, but the reaction temperature is 20 to 110 ° C., preferably 50 to 100 ° C., so that the double bond of each does not react. Is desirable.
さらに二重結合が反応しないよう、反応時に重合禁止剤を添加しておいてもよい。重合禁止剤としては、たとえば、ヒドロキノン（ＨＱ）、ヒドロキノンモノメチルエーテル（ＭＥＨＱ）、２，６−ジ−ｔ−ブチル−４−メチルフェノール（ＢＨＴ）、ｔ−ブチルカテコール（ＴＢＣ）、４−メトキシ−１−ナフトール、等のフェノール、ナフトール誘導体、フェノチアジン誘導体、ニトロソアミン塩、などが挙げられる。また、反応系中に酸素または空気を吹き込むことでも同様の重合禁止効果が得られる。重合禁止剤が着色等の問題を引き起こす場合は、重合禁止剤は少量に抑え、酸素または空気を吹き込みながら反応を行う方が好ましい。 Further, a polymerization inhibitor may be added during the reaction so that the double bond does not react. Examples of the polymerization inhibitor include hydroquinone (HQ), hydroquinone monomethyl ether (MEHQ), 2,6-di-t-butyl-4-methylphenol (BHT), t-butylcatechol (TBC), 4-methoxy- Examples thereof include phenol such as 1-naphthol, naphthol derivatives, phenothiazine derivatives, nitrosamine salts, and the like. The same polymerization inhibition effect can be obtained by blowing oxygen or air into the reaction system. When the polymerization inhibitor causes problems such as coloring, it is preferable to carry out the reaction while blowing the oxygen or air while keeping the polymerization inhibitor in a small amount.
このようにして得られる本発明の活性エネルギー線硬化性化合物（Ａ）は、アクリル系モノマー（ａ１）由来のピペリジニル基と、アクリル系モノマー（ａ２）由来のフッ素原子含有官能基と、アクリル系モノマー（ａ５）由来の（メタ）アクリロイル基を有する。活性エネルギー線硬化性化合物（Ａ）の数平均分子量は３０００〜１０００００であることが好ましく、５０００〜５００００であることがより好ましい。
プレポリマーを形成する際に用いる重合開始剤の量についての説明箇所で述べたように、多量の重合開始剤を用い、形成されるプレポリマーの数平均分子量が小さくなり過ぎると、プレポリマー中に含まれる水酸基を有しない成分の割合が多くなる。その結果、そのようなプレポリマーから形成された活性エネルギー線硬化性化合物（Ａ）中に含まれる(メタ)アクリロイル基を有しない成分の含有量が多くなり、活性エネルギー線硬化性組成物としての硬化性が悪化し、硬化塗膜の硬度等が低下してしまうため、好ましくない。
一方、活性エネルギー線硬化性化合物（Ａ）の数平均分子量が大きすぎると粘度が高くなり過ぎるため、塗料として使用する際、塗工適性が低下するおそれがある。
なお、アクリル系モノマー（ａ５）は活性エネルギー線硬化性化合物（Ａ）の数平均分子量にはほとんど影響を及ぼさないので、活性エネルギー線硬化性化合物（Ａ）の前駆体というべき、水酸基を有するプレポリマーの数平均分子量は前記したように３，０００〜１００，０００であることが好ましい。
The active energy ray-curable compound (A) of the present invention thus obtained comprises a piperidinyl group derived from the acrylic monomer (a1), a fluorine atom-containing functional group derived from the acrylic monomer (a2), and an acrylic monomer. It has a (meth) acryloyl group derived from (a5). The number average molecular weight of the active energy ray-curable compound (A) is preferably 3000 to 100,000, and more preferably 5,000 to 50,000.
As described in the explanation of the amount of the polymerization initiator used for forming the prepolymer, when a large amount of the polymerization initiator is used and the number average molecular weight of the formed prepolymer becomes too small, The ratio of the component which does not have a hydroxyl group contained increases. As a result, the content of the component having no (meth) acryloyl group contained in the active energy ray-curable compound (A) formed from such a prepolymer is increased, and the active energy ray-curable composition as an active energy ray-curable composition is obtained. This is not preferable because the curability deteriorates and the hardness of the cured coating film decreases.
On the other hand, if the number average molecular weight of the active energy ray-curable compound (A) is too large, the viscosity becomes too high, and thus the coating suitability may be lowered when used as a coating material.
The acrylic monomer (a5) has little influence on the number average molecular weight of the active energy ray-curable compound (A), so that the prepolymer having a hydroxyl group, which should be called a precursor of the active energy ray-curable compound (A), is used. The number average molecular weight of the polymer is preferably 3,000 to 100,000 as described above.
また、本発明の活性エネルギー線硬化性化合物（Ａ）は、ピペリジニル基の官能基当量が２００〜７０００であることが好ましく、３００〜４０００であることがより好ましい。
本発明の活性エネルギー線硬化性化合物（Ａ）は、フッ素原子含有官能基の官能基当量が３０００〜２００００であることが好ましく、３５００〜１７０００であることがより好ましい。
本発明の活性エネルギー線硬化性化合物（Ａ）は、（メタ）アクリロイル基の官能基当量が２５０〜１６００であることが好ましく、３００〜１０００であることがより好ましい。
なお、ここでいう官能基当量とは、各官能基１モルを含む活性エネルギー線硬化性化合物（Ａ）の質量（ｇ）を意味する。
In the active energy ray-curable compound (A) of the present invention, the functional group equivalent of the piperidinyl group is preferably 200 to 7000, and more preferably 300 to 4000.
In the active energy ray-curable compound (A) of the present invention, the functional group equivalent of the fluorine atom-containing functional group is preferably 3000 to 20000, and more preferably 3500 to 17000.
In the active energy ray-curable compound (A) of the present invention, the functional group equivalent of the (meth) acryloyl group is preferably 250 to 1600, and more preferably 300 to 1000.
In addition, a functional group equivalent here means the mass (g) of the active energy ray-curable compound (A) containing 1 mol of each functional group.
本発明の活性エネルギー線硬化性化合物（Ａ）と、他の活性エネルギー線硬化性化合物や光重合開始剤や有機溶剤等とを配合し、活性エネルギー線硬化性組成物を得ることができる。 An active energy ray-curable composition can be obtained by blending the active energy ray-curable compound (A) of the present invention with another active energy ray-curable compound, a photopolymerization initiator, an organic solvent, or the like.
他の活性エネルギー線硬化性化合物としては、ベンゾトリアゾール基と（メタ）アクリロイル基とを有する活性エネルギー線硬化性化合物（Ｂ）、前記（Ａ）〜（Ｂ）以外の他の活性エネルギー線硬化性化合物（Ｃ）を挙げることができる。 Other active energy ray-curable compounds include an active energy ray-curable compound (B) having a benzotriazole group and a (meth) acryloyl group, and other active energy ray-curable properties other than the above (A) to (B). A compound (C) can be mentioned.
ベンゾトリアゾール基と（メタ）アクリロイル基とを有する活性エネルギー線硬化性化合物（Ｂ）中のベンゾトリアゾール基は、紫外線のエネルギーを熱エネルギーに変換し、硬化塗膜中の化学結合の切断を抑制する機能を担う。
ベンゾトリアゾール基と（メタ）アクリロイル基とを有するアクリル系モノマー（Ｂ）としては、２−（２‘−ヒドロキシ−５’−（メタクリロイルオキシエチル）フェニル）−２Ｈ−ベンゾトリアゾール、２−（２‘−ヒドロキシ−３’−ｔ−ブチル−５‘−メタクリロキシエチルフェニル）−２Ｈ−ベンゾトリアゾール、２−（２’−（メタ）アクリロイルオキシ−５‘−メチルフェニル）ベンゾトリアゾール、２−（２’−（メタ）アクリロイルオキシ−５‘−ｔ−オクチルフェニル）ベンゾトリアゾール、２−（２’−（メタ）アクリロイルオキシ−３‘，５’−ジ−ｔ−ブチルフェニル）ベンゾトリアゾール等が挙げられる。
The benzotriazole group in the active energy ray-curable compound (B) having a benzotriazole group and a (meth) acryloyl group converts the energy of ultraviolet rays into thermal energy and suppresses the breakage of chemical bonds in the cured coating film. Take on the function.
Examples of the acrylic monomer (B) having a benzotriazole group and a (meth) acryloyl group include 2- (2′-hydroxy-5 ′-(methacryloyloxyethyl) phenyl) -2H-benzotriazole, 2- (2 ′ -Hydroxy-3'-t-butyl-5'-methacryloxyethylphenyl) -2H-benzotriazole, 2- (2 '-(meth) acryloyloxy-5'-methylphenyl) benzotriazole, 2- (2' -(Meth) acryloyloxy-5'-t-octylphenyl) benzotriazole, 2- (2 '-(meth) acryloyloxy-3', 5'-di-t-butylphenyl) benzotriazole and the like.
他の活性エネルギー線硬化性化合物（Ｃ）としては、（メタ）アクリロイル基を有する種々の化合物が用いられる。例えば、カプロラクトン由来の−（ＣＨ2）5−と（メタ）アクリロイル基とを有する活性エネルギー線硬化性化合物（Ｃ１）が挙げられる。カプロラクトン由来の−（ＣＨ2）5−と（メタ）アクリロイル基とを有する活性エネルギー線硬化性化合物（Ｃ１）は、下記一般式（１）にて示される構造を呈することが好ましい。 As the other active energy ray-curable compound (C), various compounds having a (meth) acryloyl group are used. Examples thereof include an active energy ray-curable compound (C1) having — (CH 2 ) 5 — derived from caprolactone and a (meth) acryloyl group. The active energy ray-curable compound (C1) having — (CH 2 ) 5 — and (meth) acryloyl group derived from caprolactone preferably has a structure represented by the following general formula (1).
一般式（１）
上記一般式（１）中、Ｒ1は、水素原子もしくはメチル基を示す。また、ｎ＋ｍ＋ｌ＋ｏ＋ｐ＋ｑ＝１〜１２の整数であり、ｎ＋ｍ＋ｌ＋ｏ＋ｐ＋ｑ＝２〜１２であることが好ましく、さらには６〜１２であることが好ましい。ｎ＋ｍ＋ｌ＋ｏ＋ｐ＋ｑが１未満では、長期の耐候性試験により塗膜が剥がれ落ちやすくなってしまう。ｎ＋ｍ＋ｌ＋ｏ＋ｐ＋ｑが１２を越えると、（メタ）アクリロイル基の量が増加し、形成される硬化塗膜の耐磨耗性が低下する傾向にある。 In the general formula (1), R1 represents a hydrogen atom or a methyl group. Moreover, it is an integer of n + m + l + o + p + q = 1-12, it is preferable that it is n + m + l + o + p + q = 2-12, and it is more preferable that it is 6-12. When n + m + l + o + p + q is less than 1, the coating film tends to peel off by a long-term weather resistance test. When n + m + l + o + p + q exceeds 12, the amount of (meth) acryloyl groups increases, and the abrasion resistance of the formed cured coating film tends to decrease.
このようなカプロラクトン由来の−（ＣＨ2）5−を有する活性エネルギー線硬化性化合物（Ｃ１）としては、ジペンタエリスリトールとε−カプロラクトンとの付加物に（メタ）アクリル酸がさらに付加したレート化物が挙げられる。 As the active energy ray-curable compound (C1) having — (CH 2 ) 5 — derived from caprolactone, a rate product obtained by further adding (meth) acrylic acid to an adduct of dipentaerythritol and ε-caprolactone. Is mentioned.
活性エネルギー線硬化性組成物は、他の活性エネルギー線硬化性化合物（Ｃ）として、カプロラクトン由来の−（ＣＨ2）5−を有しない他の活性エネルギー線硬化性化合物（Ｃ２）をさらに含有することができる。
他の活性エネルギー線硬化性化合物（Ｃ２）としては、数平均分子量が５００〜１００００のオリゴマーが好ましく、ポリエステル（メタ）アクリレート、ポリウレタン（メタ）アクリレート、エポキシ（メタ）アクリレート、（メタ）アクリル化マレイン酸変性ポリブタジエン等の不飽和二重結合を有するオリゴマーが好ましく、ポリウレタン（メタ）アクリレートがより好ましい。
これらのオリゴマーは、一分子あたりの（メタ）アクリロイル基が平均で２〜１５個であることが好ましく、さらには４〜１２個であることが好ましい。（メタ）アクリロイル基が２未満であると塗膜の硬度は低下し、耐擦傷が低下してしまう。１５個よりも多いと、塗膜の硬化収縮が大きくなり、それにつれ塗膜の歪みも大きくなる。こうした塗膜は耐候性試験時のクラック、剥離の発生につながり大きく外観を損なう。
The active energy ray-curable composition further contains, as another active energy ray-curable compound (C), another active energy ray-curable compound (C2) that does not have caprolactone-derived — (CH 2 ) 5 —. be able to.
As other active energy ray-curable compounds (C2), oligomers having a number average molecular weight of 500 to 10,000 are preferable, and polyester (meth) acrylate, polyurethane (meth) acrylate, epoxy (meth) acrylate, and (meth) acrylated maleate. Oligomers having an unsaturated double bond such as acid-modified polybutadiene are preferred, and polyurethane (meth) acrylate is more preferred.
These oligomers preferably have an average of 2 to 15 (meth) acryloyl groups per molecule, and more preferably 4 to 12. When the (meth) acryloyl group is less than 2, the hardness of the coating film is lowered and the scratch resistance is lowered. When the number is more than 15, the curing shrinkage of the coating film increases, and the distortion of the coating film increases accordingly. Such a coating film causes cracking and peeling during the weather resistance test and greatly deteriorates the appearance.
活性エネルギー線硬化性組成物は、活性エネルギー線硬化性化合物（Ａ）〜（Ｃ）の合計１００重量％中、（Ａ）：１〜５０重量％、（Ｂ）：１〜２０重量％、（Ｃ）：３０〜９５重量％であることが好ましく、（Ａ）：（Ｂ）：（Ｃ）＝２〜４５：２〜１５：４０〜９０（重量％）であることがより好ましい。
さらに活性エネルギー線硬化性化合物（Ａ）〜（Ｃ）の合計１００重量％中、（Ａ）：１〜５０重量％、（Ｂ）：１〜２０重量％、（Ｃ１）：５〜６０重量％、（Ｃ２）：２０〜８０重量％であることが好ましく、（Ａ）：（Ｂ）：（Ｃ１）：（Ｃ２）＝２〜４５：２〜１５：１０〜５０：３０〜７０（重量％）であることがより好ましい。
The active energy ray curable composition comprises (A): 1 to 50% by weight, (B): 1 to 20% by weight, in a total of 100% by weight of the active energy ray curable compounds (A) to (C). C): 30 to 95% by weight is preferable, and (A) :( B) :( C) = 2 to 45: 2 to 15:40 to 90 (% by weight) is more preferable.
Furthermore, in the total 100% by weight of the active energy ray-curable compounds (A) to (C), (A): 1 to 50% by weight, (B): 1 to 20% by weight, (C1): 5 to 60% by weight , (C2): 20 to 80% by weight, (A): (B): (C1): (C2) = 2 to 45: 2 to 15:10 to 50:30 to 70 (% by weight) ) Is more preferable.
活性エネルギー線硬化性組成物は、無機酸化物（Ｄ）をさらに含有することが塗膜の高硬度化、耐磨耗性向上の点から好ましい。無機酸化物（Ｄ）としては、ＳｉＯ2が好ましい。
具体的には、ＭＥＫ−ＳＴ、ＩＰＡ−ＳＴ、ＰＧＭ−ＳＴ（全て日産化学（株）製オルガノシリカゾル）といったアルコール、ケトン、エステル等の有機溶媒に１０〜１００ｎｍレベルのコロイダルシリカを分散させたコロイド溶液があげられる。
The active energy ray-curable composition preferably further contains an inorganic oxide (D) from the viewpoint of increasing the hardness of the coating film and improving the wear resistance. As the inorganic oxide (D), SiO 2 is preferable.
Specifically, colloidal silica in which colloidal silica of 10 to 100 nm level is dispersed in an organic solvent such as MEK-ST, IPA-ST, and PGM-ST (all of which are organosilica sols manufactured by Nissan Chemical Co., Ltd.) such as alcohol, ketone, and ester. Solution.
活性エネルギー線硬化性組成物の硬化に紫外線、可視光を用いる場合は、活性エネルギー線硬化性組成物は、さらに光重合開始剤（光ラジカル発生剤）を含有する。
活性エネルギー線硬化組成物中の活性エネルギー線硬化性化合物（Ａ）〜（Ｃ）の合計１００重量部に対して、光重合開始剤は、０．１〜２０部、好ましくは１〜１０部添加する。
光重合開始剤（光ラジカル発生剤）としては、たとえば、２，２−ジメトキシ−１，２−ジフェニルエタン−１−オン、１−ヒドロキシシクロヘキシルフェニルケトン、２−ヒドロキシ−２−メチル−１−フェニルプロパン−１−オン、１−［４−（２−ヒドロキシエトキシ）フェニル］−２−ヒドロキシ−２−メチル−１−プロパン−１−オン、２−ヒドロキシ−１−｛４−［４−（２−ヒドロキシ−２−メチルプロピオニル）ベンジル］フェニル｝−２−メチルプロパン−１−オン、２−メチル−１−（４−メチルチオフェニル）−２−モルフォリノプロパン−１−オン、２−ベンジル−２−ジメチルアミノ−１−（４−モルフォリノフェニル）ブタン−１−オン、２−（ジメチルアミノ）−２−［（４−メチルフェニル）メチル］−１−［４−（モルフォリニル）フェニル］−１−ブタノン、２，４，６−トリメチルベンゾイルジフェニルホスフィンオキサイド、ビス（２，４，６−トリメチルベンゾイル）フェニルホスフィンオキサイド、ビス（η５−２，４−シクロペンタジエン−１−イル）ビス［２，６−ジフルオロ−３−（１Ｈ−ピロール−１−イル）フェニル］チタニウム、１−［４−（フェニルチオ）フェニル］−１，２−オクタンジオン−２−Ｏ−ベンゾイルオキシム、などが挙げられる。
When ultraviolet rays and visible light are used for curing the active energy ray curable composition, the active energy ray curable composition further contains a photopolymerization initiator (photo radical generator).
The photopolymerization initiator is added in an amount of 0.1 to 20 parts, preferably 1 to 10 parts with respect to a total of 100 parts by weight of the active energy ray curable compounds (A) to (C) in the active energy ray curable composition. To do.
Examples of the photopolymerization initiator (photo radical generator) include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl phenyl ketone, and 2-hydroxy-2-methyl-1-phenyl. Propan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2 -Hydroxy-2-methylpropionyl) benzyl] phenyl} -2-methylpropan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2 -Dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1 [4- (morpholinyl) phenyl] -1-butanone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis (η5-2,4-cyclopentadiene -1-yl) bis [2,6-difluoro-3- (1H-pyrrol-1-yl) phenyl] titanium, 1- [4- (phenylthio) phenyl] -1,2-octanedione-2-O- And benzoyl oxime.
一方、硬化の際に活性エネルギー線に電子線を用いる場合は、上記のような光重合開始剤（光ラジカル発生剤）の添加は必要ない。 On the other hand, when an electron beam is used as the active energy ray at the time of curing, it is not necessary to add the photopolymerization initiator (photo radical generator) as described above.
活性エネルギー線硬化性組成物には、さらに添加剤として、熱可塑性樹脂、熱硬化性樹脂、硬化剤、レベリング剤、消泡剤、染料、顔料、酸化防止剤、重合禁止剤、保湿剤、粘度調整剤、防腐剤、抗菌剤、アンチブロッキング剤、赤外線吸収剤、電磁波シールド剤、帯電防止剤、等を加えることができる。 The active energy ray-curable composition further includes, as additives, thermoplastic resins, thermosetting resins, curing agents, leveling agents, antifoaming agents, dyes, pigments, antioxidants, polymerization inhibitors, humectants, viscosity. A regulator, preservative, antibacterial agent, antiblocking agent, infrared absorber, electromagnetic wave shielding agent, antistatic agent, and the like can be added.
各種部材に活性エネルギー線硬化性組成物を塗布し、活性エネルギー線を照射して前記組成物を硬化させることで、各種部材表面に耐候性に優れる硬化層を具備させることができる。活性エネルギー線硬化性組成物が溶剤含有する場合には、活性エネルギー線の照射に先立ち、各種部材に活性エネルギー線硬化性組成物を塗布した後、溶剤を加熱乾燥することができる。 By applying the active energy ray-curable composition to various members and irradiating the active energy rays to cure the composition, a cured layer having excellent weather resistance can be provided on the surfaces of the various members. When the active energy ray-curable composition contains a solvent, the solvent can be dried by heating after applying the active energy ray-curable composition to various members prior to the irradiation with the active energy ray.
部材としては、ガラス、セラミック、ポリカーボネート、ポリエステル、ウレタン、アクリル、ポリアセテートセルロース、ポリアミド、ポリイミド、ポリスチレン、エポキシ樹脂、ポリオレフィン、ステンレス等の各種金属、などが挙げられる。特に、ガラスやセラミックに比べて耐候性に劣る樹脂基材に使用することで、耐候性を付与することができ、用途によっては、ガラス基材にはない樹脂基材特有の軽さ、柔らかさなどを特徴生かすことができる。
形状としては、フィルムやシートや板のような平たい形状の他、高さ（厚み)のかなりある立体的な形状であってもよい。平たい形状の場合、活性エネルギー線硬化性組成物は片面又は両面に塗布することができる。また、立体的な部材の場合、部材の一部に塗布することもできるし、全表面に塗布することもできる。
Examples of the member include glass, ceramic, polycarbonate, polyester, urethane, acrylic, polyacetate cellulose, polyamide, polyimide, polystyrene, epoxy resin, polyolefin, and various metals such as stainless steel. In particular, by using a resin base material that is inferior in weather resistance compared to glass or ceramics, weather resistance can be imparted, and depending on the application, lightness and softness unique to resin base materials that are not found in glass base materials You can make use of these features.
The shape may be a flat shape such as a film, a sheet, or a plate, or a three-dimensional shape having a considerable height (thickness). In the case of a flat shape, the active energy ray-curable composition can be applied to one side or both sides. In the case of a three-dimensional member, it can be applied to a part of the member, or can be applied to the entire surface.
以下に実施例及び比較例を挙げて本発明について具体的に説明するが、本発明はこれらの実施例に限定されるものではない。なお、部、％は特に断りのない限り重量基準である。また、下記実施例及び比較例に示す活性エネルギー線硬化性組成物の性能評価は以下に示す方法で行った。 EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to these examples. Parts and% are based on weight unless otherwise specified. Moreover, the performance evaluation of the active energy ray-curable composition shown in the following Examples and Comparative Examples was performed by the method shown below.
製造例、実施例中にある略称、製品名は以下の通りである。
「ＬＡ８７」；３−（２，２，６，６−テトラメチル−４−ピペリジニル)−２−メチル−１−プロペン−３−オン（（株）ＡＤＥＫＡ社製 アデカスタブＬＡシリーズ）
「ＦＡＭＡＣ−４」；2−(パーフルオロブチル)エチルメタクリレート（ユニマテック（株）社製）
「ＦＡＭＡＣ−８」；2−(パーフルオロオクチル)エチルメタクリレート（ユニマテック（株）社製）
「ＭＭＡ」；メチルメタクリレート
「４ＨＢＡ」；４−ヒドロキシブチルアクリレート
「カレンズＡＯＩ」;（昭和電工（株）製、２−アクリロイルオキシエチルイソシアネート）
「ＲＵＶＡ９３」；２−（２’−ヒドロキシ−５’−メタクリロイルオキシエチルフェニル）−２Ｈ−ベンゾトリアゾール（大塚化学（株）社製）
「ＤＰＣＡ６０」；ジペンタエリスリトールとε−カプロラクトンとの付加物の（メタ）アクリレート化物（一般式（１）におけるｎ＋ｍ＋ｌ＋ｏ＋ｐ＋ｑ＝６）
「ＵＡ−１１００Ｈ」；ウレタンオリゴマー（新中村化学（株）社製 Ｍｎ＝７６４、官能基数＝６）
「ＰＧＭ−ＳＴ」；コロイダルシリカ（日産化学（株）社製）
「イルガキュア１８４」；１−ヒドロキシシクロヘキシルフェニルケトン（チバ・ジャパン（株）製）
「ＡＩＢＮ」；２，２’−アゾビス（イソブチロニトリル）
「ＥＨＱ」；ヒドロキノンモノメチルエーテル（和光純薬製）
「ＤＢＴＤＬ」；ジブチル錫ジラウリレート（和光純薬製）
Abbreviations and product names in production examples and examples are as follows.
“LA87”; 3- (2,2,6,6-tetramethyl-4-piperidinyl) -2-methyl-1-propen-3-one (Adeka Corporation, Adeka Stub LA series)
“FAMAC-4”; 2- (perfluorobutyl) ethyl methacrylate (manufactured by Unimatec)
“FAMAC-8”; 2- (perfluorooctyl) ethyl methacrylate (manufactured by Unimatec)
“MMA”; methyl methacrylate “4HBA”; 4-hydroxybutyl acrylate “Karenz AOI” (made by Showa Denko KK, 2-acryloyloxyethyl isocyanate)
“RUVA93”; 2- (2′-hydroxy-5′-methacryloyloxyethylphenyl) -2H-benzotriazole (manufactured by Otsuka Chemical Co., Ltd.)
“DPCA60”; (meth) acrylated product of adduct of dipentaerythritol and ε-caprolactone (n + m + l + o + p + q = 6 in the general formula (1))
“UA-1100H”; urethane oligomer (manufactured by Shin-Nakamura Chemical Co., Ltd., Mn = 764, number of functional groups = 6)
“PGM-ST”; colloidal silica (manufactured by Nissan Chemical Co., Ltd.)
“Irgacure 184”; 1-hydroxycyclohexyl phenyl ketone (manufactured by Ciba Japan Co., Ltd.)
“AIBN”; 2,2′-azobis (isobutyronitrile)
"EHQ": Hydroquinone monomethyl ether (Wako Pure Chemical Industries)
“DBTDL”: Dibutyltin dilaurate (Wako Pure Chemical Industries, Ltd.)
（実施例１）
攪拌機、温度計、還流冷却器、滴下装置、ガス導入管を備えた反応容器に、シクロヘキサノン２５０部を仕込み、窒素ガスを吹き込みながら８０℃で１時間攪拌した。滴下槽に（ａ１）としてＬＡ８７を１００部、（ａ２）としてＦＡＭＡＣ−４を２５部（ａ３）として４ＨＢＡを１２５部、ＡＩＢＮ７．５部、シクロヘキサノン８０．９部を仕込み、滴下槽内を攪拌しながら２時間かけて反応槽に滴下した。滴下終了後、シクロヘキサノン３４．７部で洗浄し、洗浄液を反応槽に入れた。さらに２時間反応させた後、ＡＩＢＮ２．５部をシクロヘキサノン２２．５部に溶かした溶液を３等分し、３０分おきに３回に分けて添加した。３回目添加の１時間後に冷却して取り出し、プレポリマーのシクロヘキサノン溶液を得た。固形分は３９．５６％であった。また、プレポリマーの水酸基価は１８５（ｍｇＫＯＨ／ｇ）であった。
Example 1
In a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a dropping device, and a gas introduction tube, 250 parts of cyclohexanone was charged and stirred at 80 ° C. for 1 hour while blowing nitrogen gas. The dripping tank was charged with 100 parts of LA87 as (a1), 25 parts of FAMAC-4 as (a2), 125 parts of 4HBA, 7.5 parts of AIBN, and 80.9 parts of cyclohexanone, and stirred in the dropping tank. Then, it was dropped into the reaction vessel over 2 hours. After completion of dropping, the solution was washed with 34.7 parts of cyclohexanone, and the washing solution was put into a reaction vessel. After further reacting for 2 hours, a solution obtained by dissolving 2.5 parts of AIBN in 22.5 parts of cyclohexanone was divided into three equal parts and added in three portions every 30 minutes. One hour after the third addition, the mixture was cooled and taken out to obtain a cyclohexanone solution of a prepolymer. The solid content was 39.56%. The hydroxyl value of the prepolymer was 185 (mgKOH / g).
上記のプレポリマーのシクロヘキサノン溶液１３７．６部、重合禁止剤としてＭＥＨＱ０．０５部、触媒としてＤＢＴＤＬ０．１７部、シクロヘキサノン３９．６部を仕込み、ドライエアーを吹き込みながら６０℃で１時間攪拌した。滴下槽に（ａ５）として、プレポリマー中の水酸基１モルに対してイソシアネート１モルに相当する量のカレンズＡＯＩを入れ、１時間かけて反応滴下した。滴下終了後、３時間後にＩＲ測定を行ったところ、イソシアネート基に由来するピークが消失していたので、冷却して取り出した。固形分は４１．５３％の活性エネルギー線硬化性化合物Ａ１の溶液を得た。
活性エネルギー線硬化性化合物Ａ１は、数平均分子量：１１０００、ピペリジニル基当量：８４２、（メタ）アクリルロイル基当量：４３０であった。
なお、数平均分子量ＭｎはＧＰＣ（ゲル浸透クロマトグラフ）を使用し、ポリスチレン換算で求めた。
137.6 parts of the cyclohexanone solution of the above prepolymer, 0.05 part of MEHQ as a polymerization inhibitor, 0.17 part of DBTDL and 39.6 parts of cyclohexanone were charged and stirred at 60 ° C. for 1 hour while blowing dry air. As (a5), Karenz AOI in an amount corresponding to 1 mol of isocyanate was added to 1 mol of hydroxyl group in the prepolymer in the dropping tank, and the reaction was dropped over 1 hour. When the IR measurement was performed 3 hours after the completion of the dropping, the peak derived from the isocyanate group had disappeared, and thus it was cooled and taken out. A solution of active energy ray-curable compound A1 having a solid content of 41.53% was obtained.
The active energy ray-curable compound A1 had a number average molecular weight of 11,000, a piperidinyl group equivalent: 842, and a (meth) acryloyl group equivalent: 430.
The number average molecular weight Mn was determined in terms of polystyrene using GPC (gel permeation chromatograph).
（製造例２〜４）、（比較製造例１〜３）
（ａ１）〜（ａ５）の種類や量を表１および表２に示すように変更した以外は製造例１と同様にして活性エネルギー線硬化性化合物Ａ２〜Ａ７の溶液を得た。
(Production Examples 2 to 4), (Comparative Production Examples 1 to 3)
Except having changed the kind and quantity of (a1)-(a5) as shown in Table 1 and Table 2, it carried out similarly to manufacture example 1, and obtained the solution of active energy ray hardening compound A2-A7.
（実施例１）
製造例１で得た各活性エネルギー線硬化性化合物Ａ１の溶液（固形分：１０重量部を含む）と、ＲＵＶＡ９３：１０重量部、ＤＰＣＡ６０：４０重量部、ＵＡ１１００Ｈ：４０重量部、ＰＧＭ−ＳＴ：７．５重量部、イルガキュア１８４：３重量部を混合し、活性エネルギー線硬化性組成物を得た。
市販ポリカーボネート板（タキロン（株）製）に前記の活性エネルギー線硬化性組成物をバーコーターにて塗工し、熱風乾燥オーブンにて１２０℃−３分間、乾燥し、その後速やかにＵＶ照射装置にてピーク照度７５０ｍＷ／ｃｍ２、積算光量１０００ｍＪ／ｃｍ２の硬化条件にて硬化させ、膜厚約１０μｍの硬化物を得た。
硬化物について、後述する方法にて、耐磨耗性、耐候性、密着性（初期、耐候性試験後）を評価した。結果を表３に示す。
Example 1
A solution of each active energy ray-curable compound A1 obtained in Production Example 1 (solid content: including 10 parts by weight), RUVA 93: 10 parts by weight, DPCA 60: 40 parts by weight, UA1100H: 40 parts by weight, PGM-ST: 7.5 parts by weight and Irgacure 184: 3 parts by weight were mixed to obtain an active energy ray-curable composition.
The above active energy ray-curable composition is applied to a commercially available polycarbonate plate (manufactured by Takiron Co., Ltd.) with a bar coater, dried in a hot air drying oven at 120 ° C. for 3 minutes, and then promptly applied to a UV irradiation apparatus. Then, it was cured under curing conditions of a peak illuminance of 750 mW / cm 2 and an integrated light quantity of 1000 mJ / cm 2 to obtain a cured product having a film thickness of about 10 μm.
About the hardened | cured material, abrasion resistance, a weather resistance, and adhesiveness (initial stage and after a weather resistance test) were evaluated by the method mentioned later. The results are shown in Table 3.
（実施例２〜６）、（比較例１〜７）
実施例１と同様にして表３〜４に示す処方に従って、活性エネルギー線硬化性組成物及び硬化物を得、同様にして評価した。
(Examples 2-6), (Comparative Examples 1-7)
The active energy ray-curable composition and the cured product were obtained in the same manner as in Example 1 according to the formulations shown in Tables 3 to 4, and evaluated in the same manner.
１）耐摩耗性
ＪＩＳ Ｋ６４０４−２２に準ずる。
具体的には、テーバー摩耗試験機（ＴＡＢＥＲ社製）を用い、摩耗輪（ＣＳ−１０Ｆ）２輪使用、５００ｇ荷重にて５００回転試験後のヘイズ変化（ΔＨ）を、ヘイズメーター（日本電色社製 ＮＤＨ２０００）を使用して測定、３箇所の測定結果の平均値に関して５段階評価を行った。
５；ΔＨ＝１０％未満
４；ΔＨ＝１０％以上２０％未満
３；ΔＨ＝２０％以上３０％未満
２；ΔＨ＝３０％以上４０％未満
１；ΔＨ＝４０％以上
1) Wear resistance Conforms to JIS K6404-22.
Specifically, using a Taber abrasion tester (manufactured by TABER), using two wear wheels (CS-10F), the haze change (ΔH) after 500 rotation tests at 500 g load, NDH2000) was used, and a five-step evaluation was performed on the average value of the measurement results at three locations.
5; ΔH = less than 10% 4; ΔH = 10% to less than 20% 3; ΔH = 20% to less than 30% 2; ΔH = 30% to less than 40% 1; ΔH = 40% or more
２）耐候性
ＪＩＳ Ｋ５６００−７−７に準ずる。
スガ試験機社製スーパーキセノンウェザーメーター（ブラックパネル温度６３℃、降雨１２分／６０分サイクル）にて試験を行い、試験後の塗膜外観（クラックの発生、自然剥離の発生）を目視で評価した。結果は試験時間と試験後の塗膜の状態に応じて以下のように５段階で評価した。
５；１０００時間の曝露試験後、外観に大きな変化がない。
４；１０００時間の曝露試験後、塗膜にクラックが発生（塗膜の剥離はなし）。
３；１０００時間の曝露試験後、塗膜に自然剥離が発生。
２；５００時間の曝露試験後、塗膜にクラックが発生（塗膜の剥離はなし）。
１；５００時間の曝露試験後、塗膜に自然剥離が発生。
2) Weather resistance Conforms to JIS K5600-7-7.
Tested with Super Xenon Weather Meter (black panel temperature 63 ° C, rainfall 12 minutes / 60 minutes cycle) manufactured by Suga Test Instruments Co., Ltd., and visually evaluated the appearance of the coating film after the test (occurrence of cracks and spontaneous peeling) did. The results were evaluated in five stages as follows according to the test time and the state of the coating film after the test.
5; No significant change in appearance after 1000 hours exposure test.
4: After 1000 hours of exposure test, cracks occurred in the coating film (the coating film was not peeled off).
3: Spontaneous peeling occurred on the coating film after 1000 hours of exposure test.
2: After 500 hours of exposure test, cracks occurred in the coating film (no peeling of the coating film).
1: After the exposure test for 500 hours, the coating film spontaneously peeled off.
３）密着性（初期）
ＪＩＳ Ｋ５６００に準ずる。
具体的には、耐候試験前の各塗膜にカッターで碁盤目（１００目）にキズを入れ、セロハンテープ（ニチバン社製２４ｍｍ幅）を密着させた後、垂直方向にはがし、塗膜が剥離せずに残存した碁盤目の数で５段階評価した。
５；１００残／１００
４；８０〜９９残／１００
３；５０〜７９残／１００
２；３０〜４９残／１００
１；０〜３０残／１００
3) Adhesion (initial)
Conforms to JIS K5600.
Specifically, scratches are made on the grid (100) with a cutter on each coating before the weather resistance test, and cellophane tape (24 mm width made by Nichiban Co., Ltd.) is adhered, then peeled off in the vertical direction, and the coating is peeled off. A five-point evaluation was made based on the number of grids that remained without.
5; 100 balance / 100
4; 80-99 remaining / 100
3; 50-79 remaining / 100
2; 30-49 remaining / 100
1; 0-30 residue / 100
４）密着性（耐候試験後）
耐候試験後の各塗膜にセロハンテープ（ニチバン社製２４ｍｍ幅）を密着させた後、垂直方向にはがし塗膜剥離の有無を評価した。結果は塗膜剥離の生じた試験時間に応じて、以下の通り５段階で評価した。
５；１０００時間の暴露試験後、塗膜の剥離がない。
４；１０００時間の曝露試験後、塗膜に剥離が発生。
３；７５０時間の曝露試験後、塗膜に剥離が発生。
２；５００時間の曝露試験後、塗膜に剥離が発生。
１；２５０時間の曝露試験後、塗膜に剥離が発生。
4) Adhesion (after weathering test)
A cellophane tape (24 mm width manufactured by Nichiban Co., Ltd.) was adhered to each coating film after the weather resistance test, and then peeled off in the vertical direction to evaluate the presence or absence of coating film peeling. The results were evaluated in five stages as follows according to the test time at which coating film peeling occurred.
5: There is no peeling of the coating film after 1000 hours of exposure test.
4: After 1000 hours of exposure test, peeling occurred on the coating film.
3: After the 750 hour exposure test, peeling occurred on the coating film.
2: After the exposure test for 500 hours, peeling occurred on the coating film.
1: After the exposure test for 250 hours, peeling occurred on the coating film.
本発明の活性エネルギー線硬化性化合物（Ａ）は、優れた硬化性と耐候性を併せ持ち、他の活性エネルギー線硬化性化合物との相溶性もよい。前記活性エネルギー線硬化性化合物（Ａ）を含有する活性エネルギー線硬化性組成物を各種部材に塗布し、硬化層を具備させることにより、紫外線等から部材を保護することができる。
そこで、活性エネルギー線硬化性組成物は、特に、屋外または屋内の太陽光が差し込む箇所など、太陽光線が照射する箇所で使用するような部材、たとえば、携帯電話、携帯ゲーム機、携帯音楽プレーヤー、デジタルカメラ等のディスプレイ、液晶テレビ、プラズマテレビのディスプレイ、太陽電池パネル、窓ガラスの表面保護フィルム、木材、紙、コンクリート、アスファルト、金属などの表面コーティング、インキ用バインダー、粘接着剤、などに使用され得る。
The active energy ray-curable compound (A) of the present invention has excellent curability and weather resistance, and has good compatibility with other active energy ray-curable compounds. By applying the active energy ray-curable composition containing the active energy ray-curable compound (A) to various members and providing a cured layer, the member can be protected from ultraviolet rays or the like.
Therefore, the active energy ray-curable composition is a member that is used in a place where sunlight is irradiated, such as a place where sunlight is shining outdoors or indoor, such as a mobile phone, a portable game machine, a portable music player, For displays such as digital cameras, LCD TVs, plasma TVs, solar panels, window glass surface protection films, wood, paper, concrete, asphalt, metal surface coatings, ink binders, adhesives, etc. Can be used.
Claims (2)
ピペリジニル基と（メタ）アクリロイル基とを有するアクリル系モノマー（ａ１）：１０〜８０重量％と、
パーフルオロアルキル基と（メタ）アクリロイル基とを有するアクリル系モノマー（ａ２）：０．１〜２０重量％と、
水酸基と（メタ）アクリロイル基とを有するアクリル系モノマー（ａ３）：１０〜８０重量％と、
必要に応じて（メタ）アクリロイル基を有するその他のアクリル系モノマー（ａ４）：０〜１０重量％とを共重合してなる、水酸基を有するアクリル系プレポリマーと、
イソシアネート基と（メタ）アクリロイル基とを有するアクリル系モノマー（ａ５）との反応生成物であり、
数平均分子量が３０００〜１０００００、
ピペリジニル基の官能基当量が２００〜７０００、
パーフルオロアルキル基の官能基当量が３０００〜２００００、
（メタ）アクリロイル基の官能基当量が２５０〜１６００である、ことを特徴とする、
ピペリジニル基と、パーフルオロアルキル基と、（メタ）アクリロイル基とを有する活性エネルギー線硬化性化合物（Ａ）。
In the following acrylic monomers (a1) to (a4) in a total of 100% by weight,
Acrylic monomer having a piperidinyl group and a (meth) acryloyl group (a1): 10 to 80% by weight;
Acrylic monomer (a2) having a perfluoroalkyl group and a (meth) acryloyl group: 0.1 to 20% by weight;
Acrylic monomer (a3) having a hydroxyl group and a (meth) acryloyl group: 10 to 80% by weight;
An acrylic prepolymer having a hydroxyl group, copolymerized with other acrylic monomer (a4) having a (meth) acryloyl group, if necessary, from 0 to 10% by weight;
It is a reaction product of an acrylic monomer (a5) having an isocyanate group and a (meth) acryloyl group,
Number average molecular weight is 3000 to 100,000,
The functional group equivalent of the piperidinyl group is 200 to 7000,
The functional group equivalent of the perfluoroalkyl group is 3000-20000,
The functional group equivalent of the (meth) acryloyl group is 250 to 1600,
An active energy ray-curable compound (A) having a piperidinyl group, a perfluoroalkyl group, and a (meth) acryloyl group.
ピペリジニル基と（メタ）アクリロイル基とを有するアクリル系モノマー（ａ１）：１０〜８０重量％と、Acrylic monomer having a piperidinyl group and a (meth) acryloyl group (a1): 10 to 80% by weight;
パーフルオロアルキル基と（メタ）アクリロイル基とを有するアクリル系モノマー（ａ２）：０．１〜２０重量％と、 Acrylic monomer (a2) having a perfluoroalkyl group and a (meth) acryloyl group: 0.1 to 20% by weight;
水酸基と（メタ）アクリロイル基とを有するアクリル系モノマー（ａ３）：１０〜８０重量％と、 Acrylic monomer (a3) having a hydroxyl group and a (meth) acryloyl group: 10 to 80% by weight;
必要に応じて（メタ）アクリロイル基を有するその他のアクリル系モノマー（ａ４）：０〜１０重量％とを共重合してなる、水酸基を有するアクリル系プレポリマーと、 An acrylic prepolymer having a hydroxyl group, copolymerized with other acrylic monomer (a4) having a (meth) acryloyl group, if necessary, from 0 to 10% by weight;
イソシアネート基と（メタ）アクリロイル基とを有するアクリル系モノマー（ａ５）とを反応させることを特徴とする、 Characterized by reacting an acrylic monomer (a5) having an isocyanate group and a (meth) acryloyl group,
数平均分子量が３０００〜１０００００、 Number average molecular weight is 3000 to 100,000,
ピペリジニル基の官能基当量が２００〜７０００、 The functional group equivalent of the piperidinyl group is 200 to 7000,
パーフルオロアルキル基の官能基当量が３０００〜２００００、 The functional group equivalent of the perfluoroalkyl group is 3000-20000,
（メタ）アクリロイル基の官能基当量が２５０〜１６００である、 The functional group equivalent of the (meth) acryloyl group is 250-1600,
ピペリジニル基と、パーフルオロアルキル基と、（メタ）アクリロイル基とを有する活性エネルギー線硬化性化合物（Ａ）の製造方法。 A method for producing an active energy ray-curable compound (A) having a piperidinyl group, a perfluoroalkyl group, and a (meth) acryloyl group.
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