JP6977698B2 - (Meta) acrylate compound, coating composition containing it and coated article - Google Patents

Description

The present invention relates to a (meth) acrylate compound, a coating composition comprising the (meth) acrylate compound, and a coated article having a coating formed using the coating composition.

Thermoplastic plastic substrates such as polycarbonate and polymethylmethacrylate generally have a number of excellent properties such as transparency, high ductility, high heat deflection temperature, and high dimensional stability. In particular, many of these materials are transparent and have traditionally been used as glass substitutes in many commercial applications.
However, these thermoplastic materials are prone to scratches and abrasions, which may reduce the transparency, and are also susceptible to deterioration by ultraviolet rays, resulting in problems such as yellowing and whitening of the surface. It will occur.

As a method for solving these problems of the thermoplastic material, a scratch resistant coating, a so-called hard coat, is provided on the surface of the resin base material.
As a general hard coat, a photocurable (meth) acrylic coating composition using a polyfunctional (meth) acrylate is known. The photocurable (meth) acrylic coating composition comprises one or more polyfunctional (meth) acrylates and a photopolymerization initiator, which is crosslinked by photopolymerization of the (meth) acrylic group in the polyfunctional (meth) acrylate. By forming a film, a hard coat that exhibits excellent scratch resistance, abrasion resistance, hardness, and chemical resistance can be obtained.
The hardcourt of this polyfunctional (meth) acrylate cured with active energy rays is resistant to scratches and abrasion, but can cause cracks and breakage throughout the thermoplastic plastic product when impacted. Often there is.
In addition, when exposed outdoors for a long period of time, cracks and deterioration chalking may occur due to a decrease in the toughness of the coating film.

To solve these problems, a method of imparting flexibility to a hard coat by using a monofunctional or double bond equivalent (meth) acrylate oligomer or monomer in combination is used (Patent Documents 1 to 3).
However, in the above method, while the impact resistance of the hard coat is increased, the flexibility and hardness of the hard coat are in a trade-off relationship, so that the hardness is significantly reduced and the scratch resistance and abrasion resistance are impaired. There is a problem that it will be lost.
As described above, it is very difficult to achieve both the hardness required for a hard coat, the flexibility to withstand an impact, and the weather crack resistance caused by a decrease in toughness due to long-term outdoor exposure.

In this regard, as a method capable of achieving both scratch resistance, abrasion resistance and impact resistance, a combination of urethane acrylate and silica fine particles using a polyalkylene glycol derivative (Patent Document 4), a tricyclodecanedimethanol skeleton. Proposed an active energy ray-curable coating agent composition using a combination of urethane (meth) acrylate and silica fine particles (Patent Document 5) and a composition containing urethane (meth) acrylate having an alicyclic structure (Patent Document 6). Has been done.

However, although the coating film produced from the compositions described in Patent Documents 4 to 6 exhibits a certain degree of scratch resistance, abrasion resistance, and impact resistance, the coating film cracks when exposed outdoors for a long period of time. And the problem of choking still remains.

In addition, as a technique using a compound having a ring structure in the main chain skeleton, an organic compound having two or more carbon-carbon double bonds in one molecule and two or more hydrogen atoms bonded to silicon atoms are contained in one molecule. Compositions for optical materials containing addition reaction products with cyclic polysiloxanes (Patent Documents 7 to 11), polycyclic hydrocarbons having two carbon-carbon double bonds in one molecule, and bonding to silicon atoms. There have been proposed compositions for optical materials (Patent Documents 12 to 15) containing an addition reaction product with a cyclic polysiloxane having three or more hydrogen atoms in one molecule.
A composition containing these components consisting of a cyclic siloxane skeleton can be obtained as a molded product having high transparency, high hardness and excellent crack resistance, but these are heat-curable forms by an addition reaction and are cured in units of several hours. I need time.

Further, a cyclic polysiloxane having a (meth) acrylic group and a perfluoropolyether group (Patent Documents 16 and 17) and a compound in which these cyclic polysiloxanes are linked by a divalent perfluoropolyether group (Patent Document 18). )It has been known.
However, these compounds are used as additives for photocurable compositions that exhibit water / oil repellency, stain resistance, and slipperiness due to the perfluoropolyether structure, and have high hardness and crack resistance. Not aimed at sex.

Japanese Unexamined Patent Publication No. 2005-255979 Japanese Patent Application Laid-Open No. 2002-212500 Japanese Unexamined Patent Publication No. 6-263809 Japanese Unexamined Patent Publication No. 2007-16215 International Publication No. 2013/114750 Japanese Unexamined Patent Publication No. 2010-215843 Japanese Unexamined Patent Publication No. 2002-324920 Japanese Unexamined Patent Publication No. 2002-327114 Japanese Unexamined Patent Publication No. 2002-327126 Japanese Unexamined Patent Publication No. 2002-338833 Japanese Unexamined Patent Publication No. 2002-341101 Japanese Unexamined Patent Publication No. 2005-89733 Japanese Unexamined Patent Publication No. 2005-15666 Japanese Unexamined Patent Publication No. 2005-272492 Japanese Unexamined Patent Publication No. 2006-63234 Japanese Unexamined Patent Publication No. 2010-53114 Japanese Unexamined Patent Publication No. 2010-138112 Japanese Unexamined Patent Publication No. 2010-285501

INDUSTRIAL APPLICABILITY The present invention has been made in view of the above circumstances, and can provide a photocurable hardcoat layer having excellent scratch resistance, tough impact resistance, and good weather resistance, particularly weather crack resistance (meth). ) It is an object of the present invention to provide an acrylate compound, a coating composition containing the same, and a coated article.

As a result of diligent studies to achieve the above object, the present inventor has found that a novel (meth) acrylate compound represented by the following general formula (1) can be easily produced in a few production steps. The composition containing this (meth) acrylate compound and various binder precursors such as a photocurable polyfunctional (meth) acrylate provides a coating film having excellent scratch resistance, crack resistance, and weather resistance. We found that and completed the present invention.

（式中、Ｒ¹、Ｒ²、Ｒ³およびＲ⁴は、それぞれ独立して、フッ素原子を含まず、かつ、酸素、窒素、硫黄およびリン原子から選ばれる少なくとも１種が介在していてもよい１価の炭化水素基、または水素原子を表し、
Ｙは、フッ素原子を含まない２価の基を表し、
Ｚ¹およびＺ²は、それぞれ独立して、フッ素原子を含まず、かつ、酸素、窒素、硫黄およびリン原子から選ばれる少なくとも１種が介在していてもよい１価の炭化水素基、（メタ）アクリロイルオキシ基を有する１価有機基、または水素原子を表すが、これらのうち少なくとも１つは（メタ）アクリロイルオキシ基を有する１価有機基であり、
ｎ１およびｎ２は、それぞれ独立して１〜５、かつ、ｎ１＋ｎ２＝３〜６を満たす整数を表し、
ｎ３およびｎ４は、それぞれ独立して１〜５、かつ、ｎ３＋ｎ４＝３〜６を満たす整数を表し、
ｍは、０〜１１の整数を表す。）
２． 前記ｍが、１〜４の整数である１の（メタ）アクリレート化合物、
３． 前記Ｚ¹およびＺ²の少なくとも一方が、下記一般式（１１）で表される基である１または２の（メタ）アクリレート化合物、
−Ｘ−（Ｔ−Ｑ）_a−（Ｐ）_b （１１）
（式中、Ｘは、それぞれ独立して、フッ素原子を含まず、かつ、酸素、窒素、硫黄およびリン原子から選ばれる少なくとも１種が介在していてもよい２〜３価の飽和炭化水素基を表し、
Ｔは、−Ｏ−（Ｃ＝Ｏ）−ＮＨ−を表し（ただし、酸素原子で前記Ｘと結合し、窒素原子で前記Ｑと結合する。）、
Ｑは、それぞれ独立して、フッ素原子を含まず、かつ、酸素、窒素、硫黄およびリン原子から選ばれる少なくとも１種が介在していてもよい２〜３価の飽和炭化水素基を表し、
Ｐは、（メタ）アクリロイルオキシ基を表し、
ａは、Ｘに結合するＴ−Ｑの数を表し、Ｘが２価の場合は１、Ｘが３価の場合は２であり、
ｂは、Ｑに結合する（メタ）アクリロイルオキシ基の数を表し、ａが１の場合は１または２、ａが２の場合は２、３または４である。）
４． 前記Ｙが、フッ素原子を含まない多環構造を有する２価の飽和炭化水素基である１〜３のいずれかの（メタ）アクリレート化合物、
５． 前記Ｙが、下記式（２ａ）〜（２ｄ）で表される２価の飽和炭化水素基から選ばれる１種または２種以上である４の（メタ）アクリレート化合物、

６． 前記Ｘが、それぞれ独立して下記式（３）または（４）で示される基である３〜５のいずれかの（メタ）アクリレート化合物、

（式中、１^*は、前記式（１）のケイ素原子と結合し、２^*は、前記式（１１）のＴであるウレタン基中の酸素原子と結合している。）
７． 前記Ｑが、それぞれ独立して下記式（５）または（６）で示される基である３〜６のいずれかの（メタ）アクリレート化合物、

（式中、３^*は、前記式（１１）のＰと結合し、４^*は、前記式（１１）のＴであるウレタン基中の窒素原子と結合している。）
８． 前記Ｒ¹〜Ｒ⁴がメチル基であり、前記Ｘが前記式（３）で示される基であり、前記ａおよびｂが１である３〜７のいずれかの（メタ）アクリレート化合物、
９． 前記ｎ１およびｎ４が３であり、ｎ２およびｎ３が１であり、ｍが１〜３の整数である１〜８のいずれかの（メタ）アクリレート化合物、
１０． 下記式（７）

（式中、Ｒ¹〜Ｒ⁴、Ｙ、ｎ１〜ｎ４、およびｍは、前記と同じ意味を表し、
Ｚ¹¹およびＺ¹²は、それぞれ独立して、フッ素原子を含まず、かつ、酸素、窒素、硫黄およびリン原子から選ばれる少なくとも１種が介在していてもよい１価の炭化水素基または水素原子を表すが、これらのうち少なくとも１つは水素原子である。）
で表される、ケイ素原子に結合した水素原子を１分子中に１個以上有する化合物と、付加反応性炭素−炭素二重結合を１分子中に１個有し、かつ、水酸基を有する化合物とを付加反応させて、下記式（８）

（式中、Ｒ¹〜Ｒ⁴、Ｙ、ｎ１〜ｎ４、およびｍは、前記と同じ意味を表し、
Ｚ²¹およびＺ²²は、それぞれ独立して、フッ素原子を含まず、かつ、酸素、窒素、硫黄およびリン原子から選ばれる少なくとも１種が介在していてもよい１価の炭化水素基、水素原子、または−Ｘ−（ＯＨ）ｇを表すが、これらのうち少なくとも１つは−Ｘ−（ＯＨ）ｇ（Ｘは、前記と同じ意味を表す。）であり、ｇは、１または２の整数を表す。）
で表される付加反応生成物を得た後、この付加反応生成物中の水酸基と、下記式（９）

（式中、ＱおよびＰは、前記と同じ意味を表し、ｈは、１または２の整数を表す。）
で表される化合物中のイソシアネート基とを反応させる３の（メタ）アクリレート化合物の製造方法、
１１． １〜９のいずれかの（メタ）アクリレート化合物および当該（メタ）アクリレート化合物以外のバインダー前駆体を含むコーティング組成物、
１２． 前記バインダー前駆体が、少なくとも１種の単官能または多官能（メタ）アクリレートと、少なくとも１種の光重合開始剤とを含む１１のコーティング組成物、
１３． 前記バインダー前駆体が、ウレタンポリ（メタ）アクリレート、並びに（メタ）アクリロイル基含有アルコキシシランの加水分解物および加水分解縮合物からなる群から選択される１種以上を含む１１または１２のコーティング組成物、
１４． さらに（メタ）アクリロイル基含有アルコキシシランで表面処理されたコロイダルシリカを含む１１〜１３のいずれかのコーティング組成物、
１５． 紫外線吸収剤、防汚剤、撥水剤、親水剤、レベリング剤、着色剤、顔料、接着促進剤、赤外線吸収剤、光安定剤、酸化防止剤、硬化触媒（ただし、上記１２の光重合開始剤を除く）、および金属酸化物微粒子（ただし、上記１４のコロイダルシリカを除く）から選ばれる１種または２種以上の添加剤を含む１１〜１４のいずれかのコーティング組成物、
１６． 基材と、この基材上に直接または少なくとも１種の他の層を介して形成された、１１〜１５のいずれかのコーティング組成物の硬化被膜とを備える被覆物品、
１７． 前記基材が、有機樹脂または木材である１６の被覆物品
を提供する。 That is, the present invention
1. 1. A (meth) acrylate compound represented by the following general formula (1),

(In the formula, R ¹ , R ² , R ³ and R ⁴ each independently contain no fluorine atom and are interspersed with at least one selected from oxygen, nitrogen, sulfur and phosphorus atoms. Represents a good monovalent hydrocarbon group, or hydrogen atom,
Y represents a divalent group containing no fluorine atom.
Z ¹ and Z ² are independently monovalent hydrocarbon groups that do not contain a hydrogen atom and may be mediated by at least one selected from oxygen, nitrogen, sulfur and phosphorus atoms (meth). ) A monovalent organic group having an acryloyloxy group, or a hydrogen atom, at least one of which is a monovalent organic group having a (meth) acryloyloxy group.
n1 and n2 represent integers that independently satisfy 1 to 5 and n1 + n2 = 3 to 6, respectively.
n3 and n4 represent integers that independently satisfy 1 to 5 and n3 + n4 = 3 to 6, respectively.
m represents an integer from 0 to 11. )
2. 2. 1 (meth) acrylate compound, wherein m is an integer of 1 to 4.
3. 3. A (meth) acrylate compound of 1 or 2, wherein ^{at least one of Z 1} and Z ² is a group represented by the following general formula (11).
-X- (T-Q) _a- (P) _b (11)
(In the formula, each of X is a 2-3 valent saturated hydrocarbon group that does not contain a fluorine atom and may contain at least one selected from oxygen, nitrogen, sulfur, and phosphorus atoms. Represents
T represents -O- (C = O) -NH- (where the oxygen atom binds to the X and the nitrogen atom binds to the Q).
Q represents a 2-3 valent saturated hydrocarbon group that is independently free of fluorine atoms and may be mediated by at least one selected from oxygen, nitrogen, sulfur and phosphorus atoms.
P represents a (meth) acryloyloxy group and represents
a represents the number of TQs bound to X, which is 1 when X is divalent and 2 when X is trivalent.
b represents the number of (meth) acryloyloxy groups attached to Q, which is 1 or 2 when a is 1 and 2, 3 or 4 when a is 2. )
4. The (meth) acrylate compound according to any one of 1 to 3, wherein Y is a divalent saturated hydrocarbon group having a polycyclic structure containing no fluorine atom.
5. 4 (meth) acrylate compounds in which Y is one or more selected from divalent saturated hydrocarbon groups represented by the following formulas (2a) to (2d).

6. The (meth) acrylate compound according to any one of 3 to 5, wherein X is a group represented by the following formula (3) or (4) independently.

(In the formula, 1 ^* is bonded to the silicon atom of the formula (1), and 2 ^* is bonded to the oxygen atom in the urethane group which is T of the formula (11).)
7. A (meth) acrylate compound according to any one of 3 to 6, wherein Q is a group represented by the following formula (5) or (6) independently.

(In the formula, 3 ^* is bonded to P in the formula (11), and 4 ^* is bonded to the nitrogen atom in the urethane group which is T in the formula (11).)
8. The (meth) acrylate compound according to any one of 3 to 7, wherein R ^{1 to} R ⁴ are methyl groups, X is a group represented by the formula (3), and a and b are 1.
9. The (meth) acrylate compound according to any one of 1 to 8, wherein n1 and n4 are 3, n2 and n3 are 1, and m is an integer of 1 to 3.
10. The following formula (7)

(In the formula, R ^{1 to} R ⁴ , Y, n1 to n4, and m have the same meanings as described above.
Z ¹¹ and Z ¹² each independently contain no fluorine atom and may be mediated by at least one selected from oxygen, nitrogen, sulfur and phosphorus atoms, and may be a monovalent hydrocarbon group or a hydrogen atom. However, at least one of these is a hydrogen atom. )
A compound having at least one hydrogen atom bonded to a silicon atom and a compound having an addition-reactive carbon-carbon double bond in one molecule and having a hydroxyl group, which are represented by. Is added to the reaction, and the following formula (8)

(In the formula, R ^{1 to} R ⁴ , Y, n1 to n4, and m have the same meanings as described above.
Z ²¹ and Z ²² are monovalent hydrocarbon groups and hydrogen atoms that are independently free of fluorine atoms and may be mediated by at least one selected from oxygen, nitrogen, sulfur and phosphorus atoms. , Or -X- (OH) g, at least one of which is -X- (OH) g (where X has the same meaning as above), where g is an integer of 1 or 2. Represents. )
After obtaining the addition reaction product represented by, the hydroxyl group in the addition reaction product and the following formula (9)

(In the formula, Q and P have the same meanings as described above, and h represents an integer of 1 or 2.)
3. A method for producing a (meth) acrylate compound, which is reacted with an isocyanate group in a compound represented by.
11. A coating composition containing a (meth) acrylate compound according to any one of 1 to 9 and a binder precursor other than the (meth) acrylate compound.
12. Eleven coating compositions, wherein the binder precursor comprises at least one monofunctional or polyfunctional (meth) acrylate and at least one photopolymerization initiator.
13. 11 or 12 coating compositions in which the binder precursor comprises one or more selected from the group consisting of urethane poly (meth) acrylates and hydrolysates and hydrolyzates of (meth) acryloyl group-containing alkoxysilanes. ,
14. The coating composition according to any one of 11 to 13, further comprising colloidal silica surface-treated with (meth) acryloyl group-containing alkoxysilane.
15. UV absorber, antifouling agent, water repellent, hydrophilic agent, leveling agent, colorant, pigment, adhesion accelerator, infrared absorber, light stabilizer, antioxidant, curing catalyst (however, the above 12 photopolymerization starts. A coating composition according to any one of 11 to 14, which comprises one or more additives selected from (excluding the agent) and metal oxide fine particles (excluding the colloidal silica of 14 above).
16. A coated article comprising a substrate and a cured coating of any of 11-15 coating compositions formed directly on the substrate or via at least one other layer.
17. 16 coated articles in which the substrate is an organic resin or wood are provided.

According to the present invention, it is possible to provide a coating composition containing a (meth) acrylate compound that provides a film having excellent crack resistance and toughness while maintaining scratch resistance.
The coating film made from the coating composition containing the (meth) acrylate compound of the present invention has a high degree of weather crack resistance.

It is a figure which shows the GPC chart of the compound (A1) used in the synthesis example, the compound (B1) and (C1) obtained in Example 1. It is a figure which shows the GPC chart of the compound (C2) and (C3) obtained in Examples 2 and 3. It is a figure which shows the IR chart of the compound (A1) used in the synthesis example, the compound (B1) and (C1) obtained in Example 1.

Hereinafter, the present invention will be specifically described.
The (meth) acrylate compound according to the present invention is characterized by being represented by the following general formula (1).

In formula (1), R ¹ , R ² , R ³ and R ⁴ each independently contain no fluorine atom and are intervened by at least one selected from oxygen, nitrogen, sulfur and phosphorus atoms. It represents a monovalent hydrocarbon group or a hydrogen atom which may be used.
The ^{monovalent hydrocarbon group of R 1 to} R ⁴ may be linear, branched or cyclic, but those having 1 to 20 carbon atoms are preferable. Specific examples thereof include alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-hexyl, cyclohexyl, n-octyl, 2-ethylhexyl and n-decyl groups; vinyl. , Alkyl groups such as allyl (2-propenyl), 1-propenyl, isopropenyl, butenyl groups; aryl groups such as phenyl, trill, xylyl, naphthyl groups; aralkyl groups such as benzyl, phenylethyl, phenylpropyl groups and the like. Be done.

Among these, a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and an aryl group having 6 to 12 carbon atoms are preferable, an alkyl group having 1 to 10 carbon atoms is more preferable, and an alkyl group having 1 to 5 carbon atoms is further preferable. Preferably, a methyl group is even more preferred.
The monovalent hydrocarbon group may have at least one selected from oxygen, nitrogen, sulfur and phosphorus atoms interposed in the molecular chain or at the end on the Si side, and for example, alkoxy having 1 to 20 carbon atoms. It may be a group.

In the formula (1), Y represents a divalent group containing no fluorine atom, and the divalent group is not particularly limited, but has a divalent structure having a polycyclic structure containing no fluorine atom. The saturated hydrocarbon groups of the above are preferable, the groups represented by the following formulas (2a) to (2d) and (10a) to (10f) are more preferable, and the groups represented by the formulas (2a) to (2d) are further more preferable. preferable.
The asymmetric divalent hydrocarbon group represented by the following formula is not limited to the following in the left-right direction, but has a structure in which each of the following formulas is rotated by 180 ° on a paper surface. May be good. Further, the hydrocarbon group represented by the following formula may be a combination of the respective structures.

In formula (1), Z ¹ and Z ² are monovalent, independently containing no fluorine atom and may be mediated by at least one selected from oxygen, nitrogen, sulfur and phosphorus atoms. Represents a hydrocarbon group, a monovalent organic group having a (meth) acryloyloxy group, or a hydrogen atom, at least one of which is a monovalent organic group having a (meth) acryloyloxy group.
Examples of the monovalent hydrocarbon group of Z ¹ and Z ² include the same groups as those exemplified in ^{R 1 to} R ^{4 above.}
The ^{monovalent organic group having a (meth) acryloyloxy group of Z 1} and Z ² is not particularly limited as long as it contains a (meth) acryloyloxy group, but in the present invention, it is particularly described below. The group represented by the formula (11) is preferable.

-X- (T-Q) a- (P) b (11)
Here, each of X independently contains a 2-3 valent saturated hydrocarbon group which does not contain a fluorine atom and may be mediated by at least one selected from oxygen, nitrogen, sulfur and phosphorus atoms. Representing, T represents a urethane group -O- (C = O) -NH- (where, an oxygen atom binds to the above X and a nitrogen atom binds to the Q), and Q is independent of each other. Represents a 2-3 valent saturated hydrocarbon group that does not contain a fluorine atom and may be mediated by at least one selected from oxygen, nitrogen, sulfur and phosphorus atoms, where P is a (meth) acryloyloxy group. Represents.

In the formula (11), the 2-3 valent saturated hydrocarbon group of X may be linear, branched or cyclic, but in consideration of the ease of synthesis, the availability of raw materials, etc., the following formula ( The group represented by 3) or (4) is preferable, and the group represented by the following formula (3) is more preferable.

（式中、１^*は、上記式（１）のケイ素原子と結合し、２^*は、上記式（１１）のＴであるウレタン基中の酸素原子と結合している。）

(In the formula, 1 ^* is bonded to the silicon atom of the above formula (1), and 2 ^* is bonded to the oxygen atom in the urethane group which is T of the above formula (11).)

In the formula (11), the 2-3 valent saturated hydrocarbon group of Q may be linear, branched, or cyclic, and specific examples thereof include −CH ₂ − and _{−CH 2} CH ₂ − (formula). (5)), −CH (CH ₃ ) CH ₂ −, − (CH ₂ ) ₄ −, −CH (CH ₃ ) CH ₂ CH ₂ −, −C (CH ₃ ) ₂ CH ₂ −, = CH −, = CHCH ₂ −, = C (CH ₃ ) CH ₂ −, −C (CH ₃ ) (CH ₂ −) ₂ (Equation (6)), etc. Saturated hydrocarbon groups of. The above "=" is not a double bond, but indicates that there are two bonds.
Among these, the group represented by the following formula (5) or (6) is preferable, and the group represented by the following formula (5) is more preferable, considering the ease of synthesis and the availability of raw materials. ..

（式中、３^*は、上記式（１１）のＰと結合し、４^*は、上記式（１１）のＴであるウレタン基中の窒素原子と結合している。）

(In the formula, 3 ^* is bonded to P in the above formula (11), and 4 ^* is bonded to the nitrogen atom in the urethane group which is T in the above formula (11).)

In formula (11), T is a urethane group-O- (C = O) -NH-, which is bonded to X by an oxygen atom in T.
Further, P is a (meth) acryloyloxy group, and is specifically represented by the following general formula (12).

（式中、Ｒ⁸は、水素原子またはメチル基を表す。）

(In the formula, R ⁸ represents a hydrogen atom or a methyl group.)

In formula (11), a represents the number of Q-Ts bound to X, 1 if X is divalent, 2 if X is trivalent, and b binds to Q (meta). ) Represents the number of acryloyloxy groups, 1 or 2 when a is 1, 2, 3 or 4 when a is 2. 1 is preferably 1 and b is preferably 1.

In the formula (1), n1 and n2 independently represent integers 1 to 5 and satisfy n1 + n2 = 3 to 6, and n3 and n4 independently represent 1 to 5 and n3 + n4 = 3, respectively. Represents an integer that satisfies ~ 6, but it is particularly preferable that n1 and n4 are 3 and n2 and n3 are 1.
Further, m represents an integer of 0 to 11, but an integer of 1 to 3 is preferable. When m is 0, Z ² is in a mode of directly bonding to the Si atom in parentheses with n2.

As the (meth) acrylate compound represented by the above formula (1), a raw material is easily available, excellent compatibility with a relatively highly polar binder precursor such as polyfunctional (meth) acrylate, and further. The compounds represented by the following (13) to (15) are preferable, but are not limited thereto, because they are excellent in photocurability.

（式中、ｍ１は、２〜１１の整数を表す。）

(In the formula, m1 represents an integer of 2 to 11.)

The (meth) acrylate compound of the present invention can be produced, for example, by a method combining a general ester exchange reaction and a urethanization reaction, and in particular, a hydrogen atom bonded to a silicon atom represented by the following formula (7) can be produced. A compound having at least one compound in one molecule and a compound having one additive-reactive carbon-carbon double bond in one molecule and having a hydroxyl group are subjected to an addition reaction and represented by the following formula (8). The method of reacting the hydroxyl group in the addition reaction product with the isocyanate group in the compound represented by the following formula (9) after preparing the addition reaction product (step 1) is preferable. be.

In each of the above equations, R ^{1 to} R ⁴ , Y, n1 to n4, m, Q, and P have the same meanings as described above, and Z ¹¹ and Z ¹² are independent of each other and do not contain a hydrogen atom. Moreover, it represents a monovalent hydrocarbon group or a hydrogen atom which may be mediated by at least one selected from oxygen, nitrogen, sulfur and phosphorus atoms, and at least one of these is a hydrogen atom, and Z ²¹ , Z ²² each independently contains a monovalent hydrocarbon group, a hydrogen atom, or a hydrogen atom which does not contain a fluorine atom and may be mediated by at least one selected from oxygen, nitrogen, sulfur and phosphorus atoms. Represents -X- (OH) g, at least one of which is -X- (OH) g (X represents the same meaning as above), where g represents an integer of 1 or 2. h represents an integer of 1 or 2. The compound represented by the formula (9) in which h exceeds 2 is difficult to synthesize and obtain.
Examples of the monovalent hydrocarbon group of Z ¹¹ , Z ¹² , Z ²¹ and Z ²² include the same groups as those exemplified in ^{R 1 to} R ^{4 above.}

(1) Step 1
The compound represented by the above formula (7) used in step 1 includes a cyclic polysiloxane skeleton and, in some cases, a divalent group Y containing no fluorine atom and a hydrogen atom bonded to a silicon atom. The compound is not particularly limited as long as it has one or more in the molecule, and specific examples thereof include 1,3,5,7-cyclotetrasiloxane and the compound represented by the following formula (16). Can be mentioned.
In step 1, the compound represented by the above formula (7) may be used alone or in combination of two or more.

（式中、ｍ２は、１〜１１の整数を表し、Ｍｅは、メチル基を意味する。）

(In the formula, m2 represents an integer of 1 to 11 and Me means a methyl group.)

On the other hand, the compound having one addition-reactive carbon-carbon double bond in one molecule and having a hydroxyl group is not particularly limited, but in the present invention, allyl alcohol and allyl glycol (ethylene glycol) are used. (Monoallyl ether), 3-allyloxy-1,2-propanediol and the like are suitable.
The amount of the compound used is preferably more than 1 mol and 10 mol or less, more preferably more than 2 mol and 5 mol or less, with respect to 1 mol of hydrogen atom bonded to a silicon atom in the compound represented by the above formula (7). ..

A catalyst may be used in the reaction of step 1.
As the catalyst, a known catalyst usually used for the hydrosilylation addition reaction can be used. For example, a carbon powder carrying a platinum metal, a second platinum chloride, a platinum chloride acid, a platinum chloride acid and a monovalent alcohol can be used. Examples thereof include a reaction product of platinum chloride, a complex of platinum chloride acid and olefins; a platinum group metal catalyst such as a palladium catalyst and a rhodium catalyst.
The amount of the catalyst used is preferably 2% by mass or less, preferably 5 to 5%, based on the total amount of the compound represented by the above formula (7), considering that side reactions are prevented and coloring of the product is prevented. 000 ppm is more preferred.

Further, in the reaction of step 1, a solvent may be used.
As the solvent, a compound represented by the above formula (7) and a solvent having one addition-reactive carbon-carbon double bond in one molecule and capable of dissolving a compound having a hydroxyl group are preferable.
As the solvent that can be used, a hydrocarbon solvent such as pentane, hexane, cyclohexane, heptane, isooctane, toluene, xylene, and mesitylen; an alcohol solvent such as methanol, ethanol, and isopropanol, acetonitrile, propionitrile, N, N-dimethylformamide. , N-Methylpyrrolidone and other aprotonic polar solvents, dichloromethane, dichloroethane, chlorobenzene and other halogenated hydrocarbon solvents; and examples thereof include ether solvents such as diethyl ether, tetrahydrofuran, dioxane, dimethoxyethane and the like. The seeds may be used alone or in combination of two or more.

The reaction temperature in step 1 is preferably 10 to 200 ° C, more preferably 20 to 150 ° C, from the viewpoint of improving productivity by shortening the reaction time and preventing side reactions to prevent coloring of the product.

(2) Step 2
The compound represented by the above formula (9) can be obtained as a commercially available product, and examples of the commercially available product include 2-acryloyloxyethyl isocyanate (trade name "Karenzu AOI", manufactured by Showa Denko KK). 1,1-Bis (acryloyloxymethyl) ethyl isocyanate (trade name "Karenzu BEI", manufactured by Showa Denko KK), 2-methacryloyloxyethyl isocyanate (trade name "Karenzu MOI", manufactured by Showa Denko KK), etc. Can be mentioned.

In the reaction of step 2, the amount of the compound represented by the above formula (9) is not particularly limited, and may be adjusted by the number of hydroxyl groups in the compound represented by the formula (8). The amount of the isocyanate group in the compound represented by the formula (9) is preferably an equimolar amount with respect to the hydroxyl group in the compound represented by the formula (8), and particularly when the isocyanate group remains, the coating composition. Since the storage stability tends to decrease when the compound is used, the ratio of the compound represented by the formula (8) and the compound represented by the formula (9) is used so that the isocyanate group does not remain in the reaction product. It is preferable to adjust.

In the urethanization reaction, a polymerization inhibitor such as p-methoxyphenol may be used in order to suppress the polymerization of the (meth) acrylicoxy group.
Further, the polymerization can be suppressed by performing the reaction atmosphere in the atmosphere or in a nitrogen atmosphere containing 4% by mass of oxygen, and these may be used in combination.

A catalyst may be used in the reaction of step 2.
As the catalyst, a known catalyst usually used for the urethanization reaction can be used, and for example, a tin-based catalyst or an amine-based catalyst can be used.
The amount of the catalyst used is relative to the total amount of the compound represented by the above formula (8) and the compound represented by the formula (9), considering that the side reaction is suppressed and the coloring of the product is prevented. 0 to 1% by mass is preferable, and 10 to 5,000 ppm is more preferable.

A solvent may be used in the reaction of step 2.
Hydrocarbon solvents such as pentane, hexane, cyclohexane, heptane, isooctane, toluene, xylene, and mesitylene can be used; aprotonic solvents such as acetonitrile, propionitrile, N, N-dimethylformamide, and N-methylpyrrolidone. Polar solvents, halogenated hydrocarbon solvents such as dichloromethane, dichloroethane, chlorobenzene, etc .; ether-based solvents such as diethyl ether, tetrahydrofuran, dioxane, dimethoxyethane, etc. may be mentioned, and these solvents may be used alone or 2 A mixture of seeds or more may be used.
In particular, as the solvent, a solvent capable of dissolving the compound represented by the above formula (8) and having no active hydrogen is preferable from the viewpoint of preventing the formation of by-products. In particular, since the coating composition can be prepared without removing the solvent from the reaction product in step 2, it is more preferable to use the solvent used when preparing the coating composition.
Further, for the purpose of removing water from the reaction system, dehydration treatment such as azeotropic dehydration or molecular sieves may be performed.

The reaction temperature in step 2 is preferably 10 to 200 ° C, more preferably 20 to 150 ° C, from the viewpoint of improving productivity by shortening the reaction time and preventing side reactions to prevent coloring of the product.

The coating composition of the present invention is composed of the above-mentioned (meth) acrylate compound of the present invention and a binder precursor other than the (meth) acrylate compound.
The binder precursor is not particularly limited as long as it is a substance other than the (meth) acrylate compound of the present invention and can be a coating binder. For example, a thermoplastic resin such as a (meth) acrylic resin or a polyurethane resin is used. Systems, photocurable (meth) acrylics consisting of monofunctional or polyfunctional (meth) acrylates, light or thermosetting epoxys consisting of monofunctional or polyfunctional epoxy compounds, thermosetting silicones with silanol, etc. Examples include various binder precursors.
Among these, a photocurable (meth) acrylic binder precursor composed of a monofunctional or polyfunctional (meth) acrylate is preferable from the viewpoint of productivity and durability.

The monofunctional or polyfunctional (meth) acrylate used as the photocurable (meth) acrylic binder precursor is not particularly limited as long as it is photocurable, and is, for example, urethane (meth) acrylate or epoxy (meth) acrylate. ) Acrylate, polyester (meth) acrylate, hydrolyzate / condensate of (meth) acryloyloxyalkoxysilane, or organic-inorganic hybrid (meth) acrylate obtained by hydrolyzing and condensing colloidal silica with (meth) acryloyloxyalkoxysilane. Examples thereof include monofunctional (meth) acrylates and polyfunctional (meth) acrylates having a polymerizable unsaturated bond such as, and may be appropriately selected depending on the required performance of the coating film.

Specific examples of the monofunctional (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, and i-butyl (meth). Acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, morpholyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate , 2-Hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycidyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, tricyclodecane (meth) acrylate, polyethylene glycol Mono (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, isobornyl (meth) acrylate, allyl (meth) acrylate, 2 -Examples include ethoxyethyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenyl (meth) acrylate, and an adduct of phthalic anhydride and 2-hydroxyethyl (meth) acrylate.

Specific examples of the polyfunctional (meth) acrylate include neopentyl glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, and polyethylene glycol (number of repeating units (hereinafter referred to as “n”) = 2 to 15) di. (Meta) acrylate, polypropylene glycol (n = 2 to 15) di (meth) acrylate, polybutylene glycol (n = 2 to 15) di (meth) acrylate, 2,2-bis (4- (meth) acryloxyethoxy) Phenyl) propane, 2,2-bis (4- (meth) acryloxidiethoxyphenyl) propane, trimethylolpropane diacrylate, bis (2- (meth) acryloxyethyl) -hydroxyethyl-isocyanurate, trimethylolpropane Tri (meth) acrylate, tris (2- (meth) acryloxyethyl) isocyanurate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta ( Meta) acrylate, dipentaerythritol hexa (meth) acrylate, epoxy poly (meth) acrylate such as epoxy di (meth) acrylate obtained by reacting bisphenol A type diepoxy with (meth) acrylic acid, 1,6-hexamethylene diisocyanate Urethane tri (meth) acrylate obtained by reacting a trimer with 2-hydroxyethyl (meth) acrylate, urethane di (meth) acrylate obtained by reacting isophorone diisocyanate with 2-hydroxypropyl (meth) acrylate, isophorone diisocyanate and pentaerythritol. Urethane hexa (meth) acrylate reacted with tri (meth) acrylate, urethane di (meth) acrylate reacted with dicyclohexyldiisocyanate and 2-hydroxyethyl (meth) acrylate, dicyclohexyldiisocyanate and poly (n = 6-15) Urethane poly (meth) acrylate such as urethane di (meth) acrylate obtained by reacting a urethanization reaction product with tetramethylene glycol with 2-hydroxyethyl (meth) acrylate, trimethylolethane and succinic acid, and (meth) acrylic acid. Polyester (meth) acrylate and trimethylol propane reacted with succinic acid, ethylene glycol and (meth) acrylic acid. Examples thereof include polyester poly (meth) acrylates such as le (meth) acrylates.

Specific examples of the organic-inorganic hybrid (meth) acrylate include 3- (meth) acryloxypropylmethyldimethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, and 2- (meth) acryloxyethyltrimethoxysilane, 2 -(Meta) acryloxyethyltriethoxysilane, (meth) acryloxymethyltrimethoxysilane, (meth) acryloxymethyltriethoxysilane, 3- (meth) acryloxypropylmethyldiethoxysilane, 3- (meth) acry A (meth) acryloyl group-containing alkoxysilane such as loxypropyltriethoxysilane, 8- (meth) acryloxyoctyltrimethoxysilane, 8- (meth) acryloxyoctyltriethoxysilane, or a mixture with other silanes. In some cases, an organic-inorganic hybrid (meth) acrylate compound obtained by (co) hydrolysis condensation in the presence of colloidal silica can be mentioned.

The photocurable (meth) acrylic binder precursor may be used alone, but it is preferable to use a plurality of the photocurable (meth) acrylic binder precursors in combination as needed.
In particular, one or two types of polyfunctional (meth) acrylates, urethane poly (meth) acrylate compounds having at least two radically polymerizable unsaturated double bonds in one molecule, and (meth) acryloyl group-containing alkoxysilanes. Combinations with one or more selected from hydrolysates or hydrolyzed condensates are suitable.
Among them, hexanediol di (meth) acrylate, mono or polypentaerythritol poly (meth) acrylate, in consideration of obtaining a coating film having excellent heat resistance, chemical resistance, durability, and adhesion to a substrate, Urethane poly (meth) acrylates with at least two radically polymerizable unsaturated double bonds in one molecule, and poly [(meth) acryloyloxyalkyl] (iso) cyanurate, (meth) acryloyloxypropylalkoxysilane alone or Organic-inorganic hybrid (meth) obtained by (co) hydrolysis / condensation of (co) hydrolyzate / condensate with other silanes, or colloidal silica with (meth) acryloyloxypropylalkoxysilane alone or with other silanes. ) A combination such as acrylate is suitable.

The content of the (meth) acrylate compound of the present invention in the coating composition of the present invention enhances the weather crack resistance of the cured coating film obtained from the composition, and also provides scratch resistance and adhesion to the substrate. Considering the increase, 1 to 100 parts by mass is preferable, and 5 to 90 parts by mass is more preferable with respect to 100 parts by mass of the total of the (meth) acrylate compound and the binder precursor.

Further, the coating composition of the present invention may contain a photopolymerization initiator.
The photopolymerization initiator may be appropriately selected from the viewpoint of compatibility and curability in the coating composition, and specific examples thereof include benzoin, benzoin monomethyl ether, benzoin isopropyl ether, acetoin, benzyl, benzophenone and p-. methoxybenzophenone, diethoxyacetophenone, benzyl dimethyl ketal, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, methylphenyl glyoxylate, 2-hydroxy-2-methyl-like of Carbonyl compounds; sulfur compounds such as tetramethylthium monosulfide, tetramethylthium disulfide; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylethoxyphosphine oxide, bis (2,4) , 6-trimethylbenzoyl) -phenylphosphine oxide, phosphate compounds such as bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphinoxide; 2-benzyl-2-dimethylamino-1 -(4-Morphorinophenyl) butanone-1, camphorquinone and the like can be mentioned. These may be used alone or in combination of two or more, and may be arbitrarily combined according to the required coating film performance.

When a photopolymerization initiator is used, its content in the composition moderates the curing rate of the obtained coating film, improves the scratch resistance and adhesion to the substrate of the cured coating film, and colors and weather resistance. In consideration of preventing deterioration of the property, 0.1 to 10 parts by mass is preferable, and 1 to 8 parts by mass is more preferable with respect to 100 parts by mass of the total of the (meth) acrylate compound and the binder precursor.

Further, other additives may be added to the coating composition of the present invention as long as the effects of the present invention are not impaired.
Such additives include UV absorbers, antifouling agents, water repellents, leveling agents, colorants, pigments, antioxidants, anti-yellowing agents, brewing agents, defoaming agents, thickeners, and sedimentation agents. Colloidal surface-treated with an inhibitor, an antistatic agent, a surfactant, an adhesion accelerator, an infrared absorber, a light stabilizer, a curing catalyst other than the above-mentioned photopolymerization initiator, and the above-mentioned (meth) acryloyl group-containing alkoxysilane. Examples thereof include metal oxide fine particles other than silica.
In particular, ultraviolet absorbers, antifouling agents, water repellents, leveling agents, colorants, pigments, adhesion promoters, infrared absorbers, light stabilizers, curing catalysts other than the above photopolymerization initiators, the above (meth) acryloyl groups. It is preferable to contain one or more additives selected from the group containing metal oxide fine particles other than colloidal silica surface-treated with the contained alkoxysilane.

Further, the coating composition of the present invention may contain an organic solvent.
The organic solvent is preferably selected and used according to the coating method.
For example, when used for spray coating, an alcohol solvent such as isobutanol, a glycol solvent such as propylene glycol monomethyl ether, an ester solvent such as n-butyl acetate, a ketone solvent such as methyl isobutyl ketone, toluene and the like. It is preferable to arbitrarily combine the above aromatic solvents to reduce the viscosity of the coating composition to 20 mPa · s or less, and when used for coating with a shower flow coat or dip coat, the viscosity of the coating composition is 100 mPa · s. It is preferable to make the following.
In the case of a high solid type coating composition having a solid content of more than 80% by mass, it is important to appropriately select a solvent in consideration of the solubility of various additives.

A cured coating film can be produced by applying the coating composition of the present invention to various substrates and curing the coating composition.
Examples of the curing method include a method of curing by heating and / or light, but photocuring is preferable from the viewpoint of productivity.
When curing with light, the coating composition is applied on the substrate so as to form a specified film thickness, and then the solvent is volatilized as necessary, and then high-pressure mercury lamps, metal halide lamps, and LEDs are used. Use a lamp or the like to irradiate ultraviolet rays or electron beams. The atmosphere to be irradiated may be air or an inert gas such as nitrogen or argon.

Examples of the base material include organic resins such as plastic molded bodies, wood-based products, fibers, ceramics, glass, metals, or composites thereof, and the present invention is not particularly limited, but the coating composition of the present invention. Can be suitably used for various plastic materials.
In particular, polycarbonate resin, polystyrene resin, acrylic resin, modified acrylic resin, urethane resin, thiourethane resin, polycondensate of halogenated bisphenol A and ethylene glycol, acrylic urethane resin, aryl halide-containing acrylic resin, sulfur-containing resin, It can be suitably used for polyalkylene terephthalate resin, cellulose resin, amorphous polyolefin resin, and composite resins thereof.

Further, those treated on the surface of these resin base materials, specifically, those treated with chemical conversion treatment, corona discharge treatment, flame treatment, plasma treatment, acid or alkaline solution, and surface layers can also be used. It is also possible to use a laminate coated with a resin of a different type from that of the base material body.
Specific examples of the laminated body include a laminated body in which an acrylic resin layer or a urethane resin layer is present on the surface layer of a polycarbonate resin base material manufactured by a coextrusion method or a laminating method, or an acrylic resin layer on the surface layer of a polyester resin base material. Examples thereof include existing laminates.
Even if the coating composition is applied directly to the surface of the substrate, it may be applied via a primer layer, an ultraviolet absorbing layer, a printing layer, a recording layer, a heat ray shielding layer, an adhesive layer, an inorganic vapor deposition film layer, or the like, if necessary. The shape may be applied.

Known coating methods include, for example, spin coaters, comma coaters, lip coaters, roll coaters, die coaters, knife coaters, blade coaters, rod coaters, kiss coaters, gravure coaters, screen coatings, dipping coatings, cast coatings and the like. It can be appropriately selected and used from the coating methods of.

The thickness of the coating film produced from the coating composition of the present invention is not particularly limited, but is 0 in consideration of preventing coating film defects, exhibiting sufficient scratch resistance, and preventing the occurrence of cracks. .1 to 50 μm is preferable, and 1 to 30 μm is more preferable in consideration of satisfactorily exhibiting the properties of coating film hardness, scratch resistance, long-term stable adhesion and crack resistance. ..

Further, if necessary, an adhesive layer, an ultraviolet absorbing layer, a printing layer, a recording layer, a heat ray shielding layer, an adhesive layer, an inorganic vapor-deposited film layer, and a water-repellent repellent layer are placed on the surface of the cured coating film of the coating composition of the present invention. Other coating layers such as an oil layer and a hydrophilic antifouling layer may be formed.

As described above, the cured coating film obtained from the coating composition of the present invention has excellent scratch resistance, but in order to obtain another scratch resistance, an inorganic thin-film film layer is coated on the coating film. You may.
The inorganic vapor deposition film layer is not particularly limited as long as it is formed by a dry film forming method, and is, for example, Si, Ti, Zn, Al, Ga, In, Ce, Bi, Sb, B, Zr. , Sn, and at least one of various metals having elements such as Ta, and a layer containing oxides, nitrides, sulfides, and the like of these metals as main components can be mentioned. Further, for example, a diamond-like carbon film layer having high hardness and excellent insulating properties can be mentioned.
The method for laminating the inorganic vapor deposition film layer is not particularly limited as long as it is a dry film deposition method, and for example, physical vapor deposition such as resistance heating vapor deposition, electron beam deposition, molecular beam epitaxy method, ion beam deposition, ion plating, and sputtering. Examples thereof include a phase growth method and a dry film deposition method such as a chemical vapor deposition method such as thermal CVD, plasma CVD, optical CVD, epitaxial CVD, atomic layer CVD, and catCVD.

The coated article thus coated with the cured product of the coating composition of the present invention can be excellent in scratch resistance and weather resistance, particularly weather crack resistance.

The coating composition of the present invention is preferably used as a photocurable coating composition for articles used outdoors.
In particular, it is preferably used for surface coating of automobile headlamp lenses, vehicle sensors, and resin glass. These substrates are polycarbonate, which is commonly used because of its high impact resistance, heat resistance, transparency and lightness. However, since polycarbonate lacks performance such as chemical resistance, weather resistance, and scratch resistance, it is preferable to coat the surface with the coating composition of the present invention to improve those performances. ..

Further, the polycarbonate coated with the coating film made of the coating composition of the present invention can prevent yellowing and weather crack resistance of the coating film, and has a surface hardness comparable to that of glass, is lightweight, and is easy to mold. It can be used for a wide variety of purposes such as automobile headlamp lenses, vehicle sensors, vehicle windows, outdoor signs, windowpanes of greenhouses and outdoor buildings, roofs of terraces and garages, balconies, and instrument covers.

Hereinafter, the present invention will be described in more detail with reference to synthetic examples, examples and comparative examples, but the present invention is not limited to these examples.
In the following examples, "parts" and "%" mean "parts by mass" and "% by mass", respectively, unless otherwise specified. The devices used in the examples are as follows.

(1) GPC measurement condition device: HLC-8320GPC manufactured by Tosoh Corporation
Column: TSKgel G4000HXL + G3000HXL + G2000HXL + G2000HXL manufactured by Tosoh Corporation (each inner diameter 6 mm, length 150 mm)
Developing solution: Tetrahydrofuran Column tank temperature: 40 ° C
Flow rate: 1 mL / min
Detector: Refractive index (RI)
Standard: Monodisperse polystyrene (2) Proton nuclear magnetic resonance spectrum ( ¹ H-NMR) Measurement conditions Device: AVANCE III 400 manufactured by BRUKER
Solvent: CDCl ₃
Internal standard: Tetramethylsilane (TMS)
(3) Infrared absorption spectrum (IR) measurement condition device: Nicolet 6700 manufactured by Thermo Fisher.

[1] Synthesis of hydrosilane compound having a cyclic siloxane skeleton [Synthesis Example 1]
To a 500 mL four-necked flask equipped with a stirrer, condenser, dropping funnel and thermometer, 80 g of toluene and 115.2 g (0.48 mol) of 1,3,5,7-tetramethylcyclotetrasiloxane were added. It was heated to 117 ° C. using an oil bath. To this, 0.05 g of carbon powder carrying 5% platinum metal was added, and while stirring, vinyl norbornene (trade name: V0062, manufactured by Tokyo Chemical Industry Co., Ltd .; 5-vinylbicyclo [2.2.1] 48 g (0.4 mol) of a mixture of isomers having a substantially equal molar amount of hept-2-ene and 6-vinylbicyclo [2.2.1] hept-2-ene) was added dropwise over 16 minutes. After completion of the dropping, the mixture was heated and stirred at 125 ° C. for 16 hours and cooled to room temperature. Then, the platinum metal-supported carbon was filtered off, and toluene was distilled off under reduced pressure to obtain a colorless and transparent viscous liquid (A1). The viscosity of this product at 25 ° C. was 2,500 mm ² / s, and the amount of SiH contained was 7.2 mmol / g on average.

As a result of analyzing the above A1 by IR, ¹ H-NMR, GPC and the like, it was found that this was a mixture shown below.
-Compound having one tetramethylcyclotetrasiloxane ring: Approximately 6 mol% (an example of a typical structural formula is shown in the following formula (17)).

-Compound having two tetramethylcyclotetrasiloxane rings: Approximately 25 mol% (an example of a typical structural formula is shown in the following formula (18)).

-Compound having three tetramethylcyclotetrasiloxane rings: Approximately 16 mol% (an example of a typical structural formula is shown in the following formula (19), m = 2).

-Has four tetramethylcyclotetrasiloxane rings: about 11 mol% (an example of a typical structural formula is shown in the above formula (19), m = 3).
-Compound having 5 to 12 cyclotetrasiloxane rings: Residual (An example of a typical structural formula is shown in the above formula (19), m = 4 to 11).

[2] Synthesis of (meth) acrylate compound [Example 1]
In a 1 L flask, 110 g (1.08 mol) of allylglycol, 0.04 g of dibutylhydroxytoluene, 0.7 g of an ethanol solution of platinum-divinyltetramethyldisiloxane complex (platinum concentration 3%), and 100 g of isopropanol are charged, and nitrogen is charged. The mixture was heated and stirred at 75 ° C. under an atmosphere. Then, 100 g (0.72 mol) of A1 obtained in the synthetic example was added dropwise over 1 hour. After completion of the dropping, the reaction was carried out at 85 ° C., followed by concentration under reduced pressure at 80 ° C. at 5 mmHg for 2 hours. After adding 273 g of toluene and 200 g of ethyl acetate to the obtained solution and stirring well, 240 g of a 10% sodium chloride aqueous solution was washed with water in three portions. The upper layer was distilled off under reduced pressure at 80 ° C. for 3 hours at 5 mmHg to obtain 152 g of a colorless and transparent viscous liquid.
The viscosity of this liquid was 170.5 Pa · s, the refractive index was 1.4820, and the hydroxyl value was 155. From the results of GPC, ¹ H-NMR, and IR, it was confirmed that this liquid was a mixture (B1, m = 1 to 11) represented by the following formula (20).

Subsequently, 100 g of the mixture (B1) obtained above, 100 g of ethyl acetate, 0.2 g of dibutylhydroxytoluene, and 0.1 g of dioctyltin oxide were placed in a 500 mL flask and charged at 80 ° C. under a 4% oxygen-nitrogen atmosphere. Was heated and stirred. Then, 58.3 g (0.41 mol) of Karenz AOI (manufactured by Showa Denko KK; 2-acryloyloxyethyl isocyanate) was added dropwise and then reacted at 80 ° C. for 5 hours. After cooling to room temperature, when IR was measured, the absorption peak (2,260 cm ^-1 ) derived from NCO almost disappeared, and the consumption of the raw material, Calends AOI, was confirmed. Then, it was filtered using a filter paper ^{to obtain 247 g of a colorless transparent liquid having a viscosity of 82.4 mm 2} / s, a non-volatile content at 105 ° C. for 3 hours, and 66.2%. From the results of GPC, ¹ H-NMR, and IR, it was confirmed that this liquid was an ethyl acetate solution of the mixture (C1, m = 1 to 11) represented by the following formula (21).

[Example 2]
A 200 mL flask was charged with 30 g of the above-mentioned mixture (B1), 50 g of ethyl acetate, 0.04 g of dibutylhydroxytoluene, and 0.03 g of dioctyltin oxide, and heated at 80 ° C. under a 4% oxygen-nitrogen atmosphere. Stirred. Then, 29 g (0.12 mol) of Karenz BEI (manufactured by Showa Denko KK; 1,1- (bisacryloyloxymethyl) ethyl isocyanate) was added dropwise, and the mixture was reacted at 80 ° C. for 5 hours. After cooling to room temperature, when IR was measured, the absorption peak (2,260 cm ^-1 ) derived from NCO almost disappeared, and the consumption of the raw material, Calends BEI, was confirmed. Then, it was filtered using a filter paper to obtain 89 g of a colorless transparent liquid having a non-volatile content at 105 ° C. for 3 hours and 64.8%. From the results of GPC, ¹ H-NMR, and IR, it was confirmed that this liquid was an ethyl acetate solution of the mixture (C2, m = 1 to 11) represented by the following formula (22).

[Example 3]
A 1 L flask is charged with 306 g (3 mol) of allylglycol, 0.08 g of dibutylhydroxytoluene, 0.9 g of an ethanol solution of platinum-divinyltetramethyldisiloxane complex (platinum concentration 3%), and 150 g of isopropanol under a nitrogen atmosphere. , Stirred by heating at 75 ° C. Then, 120 g (0.72 mol) of 1,3,5,7-tetramethylcyclotetrasiloxane was added dropwise over 1 hour. After completion of the dropping, the reaction was carried out at 85 ° C., followed by concentration under reduced pressure at 80 ° C. at 5 mmHg for 2 hours. After adding 250 g of toluene to the obtained solution and stirring well, 400 g of a 10% sodium chloride aqueous solution was washed with water in 4 portions. The upper layer was distilled off under reduced pressure at 80 ° C. for 3 hours at 5 mmHg to obtain 295 g of a colorless transparent liquid. The viscosity of this liquid was 579 mm ² / s, the refractive index was 1.4630, and the hydroxyl value was 163. From the results of GPC, ¹ H-NMR, and IR, it was confirmed that this liquid was the compound (B3) represented by the following formula (23).

Next, 162 g of compound (B3), 162 g of ethyl acetate, 0.08 g of dibutylhydroxytoluene, and 0.04 g of dioctyltin oxide were placed in a 1 L flask, and the mixture was heated and stirred at 80 ° C. under a 4% oxygen-nitrogen atmosphere. Then, 148 g (1.05 mol) of Calends AOI (manufactured by Showa Denko KK; 2-acryloyloxyethyl isocyanate) was added dropwise, and the mixture was reacted at 80 ° C. for 5 hours. After cooling to room temperature, when IR was measured, the absorption peak (2,260 cm ^-1 ) derived from NCO almost disappeared, and the consumption of the raw material, Calends BEI, was confirmed. Then, it was filtered using a filter paper to obtain 459 g of a colorless transparent liquid having a non-volatile content of 68.7% at 105 ° C. for 3 hours. From the results of GPC, ¹ H-NMR, and IR, it was confirmed that this liquid was an ethyl acetate solution of the compound (C3) represented by the following formula (24).

[Reference Example 1] Acrylosilane Hydrolyzed Condensate KBM5103 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., acryloyloxypropyltrimethoxysilane) 142 parts, isopropyl alcohol 500 parts, methquinone 0.1 parts, tetramethylammonium hydroxyside 1.0 part and 20 parts of deionized water were mixed and reacted at 20 ° C. for 24 hours to obtain a colorless and transparent liquid. It was concentrated by distillation under reduced pressure to obtain an acrylic silane hydrolyzed condensate (5103SQ) which is a colorless and transparent liquid. The non-volatile content was 99.3% and the weight average molecular weight was 1,900.

[Reference Example 2] Colloidal silica KBM5103 surface-treated with acrylic silane (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., acryloyloxypropyltrimethoxysilane) 2.8 parts, methyl ethyl ketone silica sol MEK-ST (trade name, Nissan Chemical Co., Ltd.) A mixed solution of 95.6 parts (solid content 27.4 parts) and 0.1 part of ion-exchanged water manufactured by Shin-Etsu Chemical Co., Ltd. (number average particle diameter 45 nm, silica concentration 30%) was stirred at 80 ° C. for 3 hours, and then orthoaterate. 1.4 parts of methyl ester was added, and the mixture was further heated and stirred at the same temperature for 1 hour to obtain a surface-treated silica particle dispersion. The solid content was determined to be 32%. The average particle size of the silica particles was 45 nm.

[Reference Example 3]
Using the method described in Example 6 of JP-A-2003-327626, SPHEA, a reaction product of 1,4-bis (dimethylchlorosilyl) benzene represented by the following formula and 2-hydroxyethyl acrylate, was prepared. Synthesized.

[Reference example 4]
Using the method described in Example 3 of JP-A-2003-327626, 1,4-bis (dimethylchlorosilyl) benzene and 3- (acryloyloxy) -2-hydroxypropyl meta represented by the following formulas are used. The reaction product SPAMA with acrylate was synthesized.

[3] Preparation of coating composition [Example 4]
8.6 parts of the mixture (C1) obtained in Example 1, 4 parts of Aronix M403 (manufactured by Toa Synthetic Co., Ltd., dipentaerythritol penta and hexaacrylate), HDDA (manufactured by Daisel Cytec, 1,6-hexanediol). Diacrylate) 2.5 parts, IRGACURE184 (BASF polymerization initiator, 1-hydroxycyclohexylphenylketone) 0.23 parts, LUCILIN TPO (BASF polymerization initiator, 2,4,6-trimethylbenzoyldiphenylphosphine) 0.23 parts of oxide), 0.02 part of KP341 (manufactured by Shinetsu Chemical Industry Co., Ltd., polyether-modified silicone) as a leveling agent, 2.5 parts of TINUVIN400 (manufactured by BASF, triazine-based ultraviolet absorber) as an ultraviolet absorber. , 17.4 parts of propylene glycol monomethyl ether was blended as a solvent to prepare a photocurable coating composition (D1).

[Examples 5 to 13, Comparative Examples 1 to 6]
The coating composition (D2 to D10, R1 to R6) using the compounds obtained in Examples 1 to 3 and the compounds of Reference Examples 1 to 4 in the same manner as in Example 4 with the formulations shown in Tables 1 and 2. ) Was prepared. These coating compositions are applied to the surface of a polycarbonate NF-2000 sheet (thickness 4 mm × length 15 cm × width 10 cm) manufactured by Mitsubishi Engineering Plastics Co., Ltd. by a flow coating method, air-dried for 5 minutes, and further heated to 80 ° C. After heating for 1 minute, the coating film was cured by irradiating with light at an irradiation amount of ^{600 mJ / cm 2} using a high-pressure mercury lamp to obtain a test piece.

The following evaluations were performed on the coating films obtained in the above Examples and Comparative Examples. The results are shown in Table 1.
(1) Appearance of coating film The coating film was visually observed to determine the presence or absence of abnormality.
◯: No abnormality △: Coloring ×: Foreign matter, unevenness, whitening abnormality (2) Initial haze The fogging value of the coating sheet was measured using the haze meter NDH5000SP manufactured by Nippon Denshoku Kogyo Co., Ltd., and the initial haze. And said.
(3) Scratch resistance According to ASTM1044, the wear wheel CS-10F is attached with a tabor wear tester, the fogging value after 500 rotations under a load of 500 g is measured, and the difference in fogging value after and before the test is tolerated. It was scratch-resistant.
(4) Initial adhesion According to JIS K5600, 25 grids are made by making vertical and horizontal 6 cuts in the coating film at 2 mm intervals using a razor blade, and cellophane tape (registered trademark, Nichiban Co., Ltd.) The number of squares (X) remaining without peeling of the coating film when the coating film was rapidly peeled off 90 ° in front of the surface after the product) was well adhered was indicated by X / 25.
(5) Boiling Adhesion Evaluation The adhesion of the sample after being immersed in boiling water for 2 hours was evaluated in the same manner as the above initial adhesion.
(6) Weather resistance evaluation Using IWASAKI ELECTRIC CO., LTD. Eye Super UV Tester W-151, [Black panel temperature 63 ° C, humidity 50% RH, illuminance 50 mW / cm ² , rainfall 10 seconds / hour for 5 hours ] → [Black panel temperature 30 ° C., humidity 95% RH for 1 hour] was set as one cycle, and tests were conducted for 100 hours, 200 hours, and 300 hours under the condition of repeating this cycle. The state of the coating film after the weather resistance test was observed visually or with a microscope (magnification 250 times) and evaluated according to the following criteria.
○: No abnormality △: Slightly abnormal (crack, whitening, or partial peeling)
×: There are cracks, whitening, or peeling on the entire coating film. Also, the yellowing degree at each time is measured using a color difference meter 300A manufactured by Nippon Denshoku Kogyo Co., Ltd., and the difference from the initial yellowing degree is obtained. This was defined as the change in yellowing degree (ΔYI).

The abbreviations in Tables 1 and 2 are as follows.
Other Acrylate SPHEA: Reaction product of 1,4-bis (dimethylchlorosilyl) benzene synthesized by the method described in Example 6 of JP-A-2003-327626 and 2-hydroxyethyl acrylate (see Reference Example 3).
SPAMA: Reaction product of 1,4-bis (dimethylchlorosilyl) benzene synthesized by the method described in Example 6 of JP-A-2003-327626 and 3- (acryloyloxy) -2-hydroxypropyl methacrylate (reference). See Example 4)
BPADA: ABE-300 (trade name, manufactured by Shin Nakamura Chemical Industry Co., Ltd., ethoxylated bisphenol A diacrylate)
TCDDA: A-DCP (trade name, manufactured by Shin Nakamura Chemical Industry Co., Ltd., tricyclodecanedimethanol diacrylate)
A-M403: Aronix M403 (trade name, manufactured by Toagosei Co., Ltd., dipentaerythritol penta and hexaacrylate)
HDDA: HDDA (trade name, manufactured by Dycel Cytec, 1,6-hexanediol diacrylate)
U-4HA: Urethane acrylate U-4HA (trade name, manufactured by Shin Nakamura Chemical Industry Co., Ltd., non-yellowing type)
5103SQ: Hydrolyzed condensate of KBM5103 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., 3-acryloxypropyltrimethoxysilane) (see Reference Example 1).
Photopolymerization Initiator I184: IRGACURE184 (trade name, manufactured by BASF, 1-hydroxycyclohexylphenyl ketone)
L-TPO: LUCIRIN-TPO (trade name, manufactured by BASF, 2,4,6-trimethylbenzoyldiphenylphosphine oxide)
Additive KP341: KP341 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., polyether-modified silicone)
Silica: Silica particle dispersion liquid surface-treated with KBM5103 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., acryloyloxypropyltrimethoxysilane) (see Reference Example 2).
T400: TINUVIN400 (trade name: BASF, hydroxyphenyltriazine-based UV absorber)
Solvent PGM: Propylene glycol monomethyl ether

As shown in Tables 1 and 2, the coating films prepared in Examples 4 to 13 (D1 to D10) were prepared in Comparative Examples 1 and 2 (R1, R2) containing no (meth) acrylate compound of the present invention. Although the scratch resistance was inferior to that of the coating film, the weather resistance, especially the weather crack resistance, was significantly improved.
Surprisingly, it can be seen that the larger the amount of the (meth) acrylate compound of the present invention, the smaller the change in yellowing degree (ΔYI) after the weather resistance test.
Further, it can be seen that the coating films prepared in Examples 6 to 13 (D3 to D10) containing the surface-treated silica have improved scratch resistance while maintaining weather crack resistance.
The coating obtained from the coating composition containing the (meth) acrylate having one cyclotetrasiloxane of Examples 12 and 13 (D9, D10) is a plurality of cyclotetrasiloxanes of Examples 4 to 11 (D1 to D8). It can be seen that the weather resistance is slightly inferior to that of the (meth) acrylate having.

On the other hand, the coating film prepared in Comparative Examples 1 to 6 (R1 to R6) in which another (meth) acrylate was blended in place of the (meth) acrylate of the present invention had scratch resistance of Examples 4 to 7 (D1 to D4). ), But it can be seen that it is significantly inferior in boiling adhesion and weather resistance. It is presumed that this is because the main chain in the (meth) acrylate compound of the present invention is rigid, which reduces the degree of freedom of the (meth) acrylic crosslinked portion, and thus the crack resistance is improved.
From these results, the effect of the (meth) acrylate compound of the present invention is clear.

Claims (14)

A (meth) acrylate compound represented by the following general formula (1).

(In the formula, R ¹ , R ² , R ³ and R ⁴ independently represent a fluorine atom-free alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 12 carbon atoms or a hydrogen atom, respectively.
Y represents a divalent saturated hydrocarbon group having a polycyclic structure containing no fluorine atom, and is a divalent saturated hydrocarbon represented by the following formulas (2a) to (2d) and (10a) to (10f). One or more selected from the group,
Z ¹ and Z ² are independently an alkyl group having 1 to 20 carbon atoms containing no fluorine atom, an aryl group having 6 to 12 carbon atoms, and a (meth) acryloyloxy group represented by the following formula (11). Represents a monovalent organic group having a hydrogen atom, or at least one of these is a monovalent organic group having the (meth) acryloyloxy group.
n1 and n2 represent integers that independently satisfy 1 to 5 and n1 + n2 = 3 to 6, respectively.
n3 and n4 represent integers that independently satisfy 1 to 5 and n3 + n4 = 3 to 6, respectively.
m represents an integer of 1 to 4. )

-X- (T-Q) _a- (P) _b (11)
(In the formula, X independently represents a 2-3 valent saturated hydrocarbon group that does not contain a fluorine atom and may be interspersed with an oxygen atom.
T represents -O- (C = O) -NH- (where the oxygen atom binds to the X and the nitrogen atom binds to the Q).
Q independently represents a linear or branched 2-3 valent saturated hydrocarbon having 1 to 5 carbon atoms and does not contain a fluorine atom.
P represents a (meth) acryloyloxy group and represents
a represents the number of TQs bound to X, which is 1 when X is divalent and 2 when X is trivalent.
b represents the number of (meth) acryloyloxy groups attached to Q, which is 1 or 2 when a is 1 and 2, 3 or 4 when a is 2. ) The (meth) acrylate compound according to claim 1, wherein Y is one or more selected from divalent saturated hydrocarbon groups represented by the following formulas (2a) to (2d).

The (meth) acrylate compound according to claim 1 or 2, wherein X is a group independently represented by the following formula (3) or (4).

(In the formula, 1 ^* is bonded to the silicon atom of the formula (1), and 2 ^* is bonded to the oxygen atom in the urethane group which is T of the formula (11).) The (meth) acrylate compound according to any one of claims 1 to 3, wherein the Q is a group represented by the following formula (5) or (6) independently.

(In the formula, 3 ^* is bonded to P in the formula (11), and 4 ^* is bonded to the nitrogen atom in the urethane group which is T in the formula (11).) The (meth) acrylate compound according to claim 3 or 4, wherein R ^{1 to} R ⁴ are methyl groups, X is a group represented by the formula (3), and a and b are 1. The (meth) acrylate compound according to any one of claims 1 to 5, wherein n1 and n4 are 3, n2 and n3 are 1, and m is an integer of 1 to 3. The following formula (7)

(In the formula, R ^{1 to} R ⁴ , Y, n1 to n4, and m have the same meanings as described above.
Z ¹¹ and Z ¹² independently represent a fluorine atom-free alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 12 carbon atoms, or a hydrogen atom, at least one of which is a hydrogen atom. Is. )
A compound having at least one hydrogen atom bonded to a silicon atom and a compound having an addition-reactive carbon-carbon double bond in one molecule and having a hydroxyl group, which are represented by. Is added to the reaction, and the following formula (8)

(In the formula, R ^{1 to} R ⁴ , Y, n1 to n4, and m have the same meanings as described above.
Z ²¹ and Z ²² independently represent an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 12 carbon atoms, a hydrogen atom, or -X- (OH) g, which do not contain a fluorine atom. At least one of these is -X- (OH) g (where X has the same meaning as above), where g represents an integer of 1 or 2. )
After obtaining the addition reaction product represented by, the hydroxyl group in the addition reaction product and the following formula (9)

(In the formula, Q and P have the same meanings as described above, and h represents an integer of 1 or 2.)
The method for producing a (meth) acrylate compound according to claim 1, wherein the reaction is carried out with an isocyanate group in the compound represented by. A coating composition containing the (meth) acrylate compound according to any one of claims 1 to 6 and a binder precursor other than the (meth) acrylate compound. The coating composition of claim 8, wherein the binder precursor comprises at least one monofunctional or polyfunctional (meth) acrylate and at least one photopolymerization initiator. The eighth or nine claim, wherein the binder precursor comprises one or more selected from the group consisting of a urethane poly (meth) acrylate and a hydrolyzate and a hydrolyzed condensate of a (meth) acryloyl group-containing alkoxysilane. Coating composition. The coating composition according to any one of claims 8 to 10, further comprising colloidal silica surface-treated with (meth) acryloyl group-containing alkoxysilane. UV absorber, antifouling agent, water repellent, hydrophilic agent, leveling agent, colorant, pigment, adhesion accelerator, infrared absorber, light stabilizer, antioxidant, curing catalyst (however, the light according to claim 9). The invention according to any one of claims 8 to 11, which comprises one or more additives selected from (excluding the polymerization initiator) and the metal oxide fine particles (excluding the colloidal silica according to claim 11). Coating composition. A coated article comprising a substrate and a cured coating of the coating composition according to any one of claims 8-12, formed directly on the substrate or via at least one other layer. The coated article according to claim 13, wherein the base material is an organic resin or wood.

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