JP6156214B2 - Reactive ultraviolet absorber, method for producing the same, and coating composition and coated article containing the same - Google Patents

Description

  The present invention relates to a novel ultraviolet absorber and a method for producing the same, a coating composition containing the ultraviolet absorber, and a coated article using the composition.

  Thermoplastic substrates such as polycarbonate and polymethylmethacrylate are generally characterized by a number of excellent properties such as transparency, high ductility, high heat deflection temperature, and dimensional stability. Many of these materials are transparent and are traditionally used as glass substitutes in a number of commercial applications. However, these materials are liable to cause scratches and wear scars, and thus the transparency may be lowered. Moreover, it is susceptible to deterioration by ultraviolet rays. As a result, problems such as yellowing of the substrate and whitening of the surface occur. As a method for solving these problems, a film made of a scratch-resistant coating containing an ultraviolet absorber is provided on the surface of the resin substrate.

  However, the scratch-resistant coating film containing such an ultraviolet absorber does not exhibit its performance sufficiently due to bleeding out or spilling of the ultraviolet absorber, or the original scratch-resistant performance is obtained by adding the ultraviolet absorber. There was a problem that it would decrease. In order to overcome these problems, a UV absorber is bound and fixed to the binder component of the scratch-resistant coating film, thereby suppressing deterioration in weather resistance and scratch resistance due to bleeding out or outflow. Has been done. At this time, it is necessary to design the ultraviolet absorber according to the main chain structure and the crosslinking type of the scratch-resistant coating binder.

  For example, a silicone hard coat composition having good scratch resistance and durability can be cured and a film can be obtained by crosslinking a precursor comprising a hydrolysis condensate of alkoxysilane by a crosslinking reaction by silanol (SiOH) condensation. Examples of ultraviolet absorbers in which a reactive group capable of silanol crosslinking is introduced into such a silicone hard coat composition include Patent Documents 1 to 4 (Japanese Patent Publication Nos. 3-14862 and 3-62177, (Kaihei 7-278525, JP2012-526159) are known. However, these reactive silylated UV absorbers have process problems such as multi-step synthesis route and removal of hydrosilylation catalyst. In general, a silicone hard coat film must be laminated on a resin substrate through a primer, so that sufficient adhesion cannot be obtained, and thus a process such as production of a primer or coating and curing is separately required. .

  As another example of the scratch-resistant coating, a photocurable (meth) acrylic coating composition is known. The photocurable (meth) acrylic coating composition contains one or more polyfunctional (meth) acrylates and a photopolymerization initiator, and is crosslinked by photopolymerization of (meth) acrylic groups in the polyfunctional (meth) acrylate. A coating can be obtained. Examples of ultraviolet absorbers in which reactive groups have been introduced to such photo-curable (meth) acrylic coating compositions have been reported (Patent Documents 5 to 9: US Pat. No. 4,750,914, JP 2012). No. 167288, JP 2010-270230, JP 2012-219102, JP 2012-31434). The photo-curable (meth) acrylic coating composition containing these reactive group-introduced UV absorbers can be applied directly to the resin substrate without the need for a primer that has become a problem with the above silicone hard coat composition. Although it can be cured, there are still problems that cannot be solved.

  Patent Documents 5 and 6 exemplify alkoxysilyl group-containing dibenzoylresorcinol derivatives as ultraviolet absorbers into which reactive groups have been introduced. In this case, since the alkoxysilyl group does not participate in the crosslinking reaction of the photocurable (meth) acrylic coating, it is considered that the scratch resistance when formed into a film is lowered, and there is actually no description regarding the scratch resistance. Further, in terms of long-term weather resistance, the UV absorber is considered not to react with the binder, so there is a concern of bleeding out.

  Patent Documents 7 and 8 exemplify silsesquioxanes having a (meth) acryl functional benzotriazole ultraviolet absorbing group. The UV absorber has improved solubility in polyfunctional (meth) acrylates compared to unmodified benzotriazole type UV absorbers, but there are parts that do not contribute to UV absorption such as silsesquioxane skeletons. Relatively many. That is, if the proportion of the UV-absorbing group per molecular weight of the molecule is the UV-absorbing group content, the UV-absorbing group content will be small. The compounding amount of the agent inevitably increases, and the performance other than the weather resistance such as scratch resistance and adhesion of the coating film tends to decrease.

  In Patent Document 9, there is an example of a photocurable (meth) acrylic polymer having an ultraviolet absorbing group and a (meth) acryloyl group in the side chain. This (meth) acrylic polymer reacts with the polyfunctional (meth) acrylate in the photocurable (meth) acrylic coating composition and is fixed in the coating. Although the ultraviolet absorber also has improved solubility in polyfunctional (meth) acrylate, it is a polymer, so the content of UV-absorbing groups is reduced, and the compounding amount is increased, so the scratch resistance and adhesion are also reduced. Tend to.

  On the other hand, examples of (meth) acrylic functional ultraviolet absorbers having a large ultraviolet absorbing group content and relatively low molecular weight are also known. A commercially available example is 2- [2'-hydroxy-5 '-(methacryloyloxyethyl) phenyl] -2H-benzotriazole (trade name "RUVA-93" manufactured by Otsuka Chemical Co., Ltd.). Further, a benzotriazole type ultraviolet absorber (Patent Document 10: Japanese Patent Laid-Open No. 6-88065) and an benzophenone type ultraviolet absorber (Patent Document 11: Special) in which unsaturated double bonds are linked by urethane bonds via an alkylene chain. Kaihei 6-88066) is exemplified. Further, examples of benzotriazine type ultraviolet absorbers to which (meth) acryl functionalization is bonded are also disclosed (Patent Documents 12 to 14: JP-A-4-214785, JP-A-9-28785, International Publication No. 2007/105741). These relatively low molecular weight (meth) acryl functionalized UV absorbers are suitable for synthesizing (meth) acrylic polymers such as Patent Document 9 because there is one (meth) acrylic group in one molecule. However, the UV-absorbing agent for the scratch-resistant photocurable (meth) acrylic coating composition is not preferable because the crosslinking density is lowered and as a result, the scratch resistance is lowered.

  In general, benzophenone-type and resorcinol-type UV absorbers have insufficient UV-absorbing performance, and it is known that certain benzotriazole-type UV absorbers may be toxic. Moreover, the benzotriazole type ultraviolet absorber having no safety problem has low solubility and has a limited amount.

  Thus, in the photo-curable (meth) acrylic coating composition that can be directly applied to the resin substrate without the need for a primer, it has good solubility in polyfunctional (meth) acrylate and has a large UV-absorbing group content. Also, from the viewpoint of not impairing the scratch resistance and adhesion of the coating film, a (meth) acryl functional UV absorber that has been sufficiently satisfied has not been known so far.

Japanese Patent Publication No. 3-14862 Japanese Patent Publication No. 3-62177 JP-A-7-278525 Special table 2012-526159 gazette U.S. Pat. No. 4,750,914 JP 2012-167288 A JP 2010-270230 A JP 2012-219102 A JP 2012-31434 A JP-A-6-88065 JP-A-6-88066 JP-A-4-214785 JP-A-9-28785 International Publication No. 2007/105741

  The present invention has been made in view of the above circumstances, and exhibits excellent ultraviolet absorption and solubility in polyfunctional (meth) acrylates, and a novel benzotriazine type ultraviolet absorption having a plurality of (meth) acryloxy groups. It aims at providing an agent and its manufacturing method. Also, by using this ultraviolet absorber, a coating composition that is excellent in scratch resistance and adhesion, and can be stably held in a coating film without causing bleed-out, etc., and Another object is to provide a coated article formed by coating with a cured film.

  As a result of intensive studies to achieve the above object, the present inventors have obtained a novel ultraviolet absorber represented by the following general formula (1), which has not been known so far, in a few production steps, The product can be easily produced, and excellent crosslinking is achieved by combining the UV absorber as a (meth) acryl-functionalized UV absorber with various binder precursors such as a photo-curable polyfunctional (meth) acrylate. It has been found that it can be a coating composition having density, ultraviolet absorption, bleed-out resistance and storage stability, and has led to the present invention.

｛式中、Ｙ¹及びＹ²は互いに独立して、一般式（２）の置換基であり、

＊は結合部位を示し、ｒは０又は１であり、
Ｒ¹、Ｒ²、Ｒ³は互いに独立して、水素原子、水酸基、炭素数１〜２０のアルキル基、炭素数４〜１２のシクロアルキル基、炭素数２〜２０のアルケニル基、炭素数１〜２０のアルコキシ基、炭素数４〜１２のシクロアルコキシ基、炭素数２〜２０のアルケニルオキシ基、炭素数７〜２０のアラルキル基、ハロゲン原子、−Ｃ≡Ｎ、炭素数１〜５のハロアルキル基、−ＳＯ₂Ｒ’、−ＳＯ₃Ｈ、−ＳＯ₃Ｍ（Ｍ＝アルカリ金属）、−ＣＯＯＲ’、−ＣＯＮＨＲ’、−ＣＯＮＲ’Ｒ”、−ＯＣＯＯＲ’、−ＯＣＯＲ’、−ＯＣＯＮＨＲ’、（メタ）アクリルアミノ基、（メタ）アクリルオキシ基、又は置換されていてもよい炭素数６〜１２のアリール基又は炭素数３〜１２のヘテロアリール基であり、
Ｒ’及びＲ”は水素原子、炭素数１〜２０のアルキル基、炭素数４〜１２のシクロアルキル基、又は置換されていてもよい炭素数６〜１２のアリール基又は炭素数３〜１２のヘテロアリール基を示し、
Ｘは２〜４価の直鎖又は分岐の酸素、窒素、硫黄及びリン原子のうち少なくとも１種が介在していてもよい飽和炭化水素残基であり、
Ｔはウレタン基−Ｏ−（Ｃ＝Ｏ）−ＮＨ−を表し、
Ｑは２〜３価の直鎖又は分岐の酸素、窒素、硫黄及びリン原子のうち少なくとも１種が介在していてもよい飽和炭化水素残基であり、
Ｐは（メタ）アクリルオキシ基であり、
ｍは１又は２であり、
ｎは１〜３の整数であるが、ｍとｎとが同時に１であることはない。｝
［２］ Ｘは下記一般式（３）又は（４）で示される基であり、Ｑは下記一般式（５）又は（６）で示される基であることを特徴とする［１］記載の反応性紫外線吸収剤。

｛式中、＊１は前記式（１）中の酸素と結合しており、＊２は前記式（１）中のＴと結合しており、＊３は互いに独立して、水素原子、又は直接あるいは直鎖もしくは分岐の酸素、窒素、硫黄及びリン原子のうち少なくとも１種が介在していてもよい２価の飽和炭化水素基を介して上記式（１）中のＴと結合しており、＊３の少なくとも１つは直接あるいは直鎖もしくは分岐の酸素、窒素、硫黄及びリン原子のうち少なくとも１種が介在していてもよい２価の飽和炭化水素基を介してＴと結合している。｝

｛式中、＊４は前記式（１）中のＴと結合しており、＊５は前記式（１）中のＰと結合している。｝
［３］ 前記式（１）において、Ｒ¹、Ｒ²、Ｒ³は互いに独立して、水素原子又はメチル基であり、
Ｘは前記式（３）で示される基であり、
Ｑは前記式（６）で示される基であり、
ｍは２であり、
ｎは１であることを特徴とする［２］記載の反応性紫外線吸収剤。
［４］ 下記工程（ＩＩ）を含むことを特徴とする［１］〜［３］のいずれかに記載の反応性紫外線吸収剤の製造方法。
（ＩＩ）下記式（７）で表される前駆化合物のＸと結合した水酸基と、

｛式中、Ｙ¹、Ｙ²、Ｘ、ｎは前記と同一である。｝
下記式（８）で表される化合物のイソシアネート基とを反応させる工程。

｛式中、Ｑ、Ｐ、ｍは前記と同一である。｝
［５］ 下記工程（Ｉ）を経た後に、前記工程（ＩＩ）を行うことを特徴とする［４］記載の反応性紫外線吸収剤の製造方法。
（Ｉ）前記式（１）において、Ｘが［２］記載の式（４）である場合、下記式（９）で表されるエステル化合物と、

｛式中、Ｙ¹、Ｙ²は前記と同一であり、Ｒ⁴は１価の直鎖又は分岐の酸素、窒素、硫黄及びリン原子のうち少なくとも１種が介在していてもよい飽和炭化水素基である。｝
下記式（１０）で表される多価アルコール化合物とをエステル交換反応させて、前記式（７）の前駆化合物を得る工程。

｛式中、Ｒ⁵、Ｒ⁶、Ｒ⁷は独立して、水素原子、水酸基、直鎖もしくは分岐の酸素、窒素、硫黄及びリン原子のうち少なくとも１種が介在していてもよい１価の飽和炭化水素基、又は直鎖もしくは分岐の酸素、窒素、硫黄及びリン原子のうち少なくとも１種が介在していてもよい末端に水酸基が結合した１価の飽和炭化水素基であって、少なくとも１つは水酸基又は直鎖もしくは分岐の酸素、窒素、硫黄及びリン原子のうち少なくとも１種が介在していてもよい末端に水酸基が結合した飽和炭化水素基である。｝
［６］ ［１］〜［３］のいずれかに記載の反応性紫外線吸収剤及びバインダー前駆体を含むコーティング組成物。
［７］ バインダー前駆体が少なくとも１種の単官能又は多官能（メタ）アクリレートを含み、更に少なくとも１種の光重合開始剤を含むことを特徴とする［６］記載のコーティング組成物。
［８］ 前記バインダー前駆体がウレタンポリ（メタ）アクリレート及び（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又は加水分解縮合物からなる群から選択される１種以上を含むことを特徴とする［７］記載のコーティング組成物。
［９］ 更に、前記バインダー前駆体が、コロイダルシリカと（メタ）アクリル官能性アルコキシシランとを加水分解・縮合して得られる有機無機ハイブリッド（メタ）アクリレートを含むことを特徴とする［７］又は［８］記載のコーティング組成物。
［１０］ 防汚剤、撥水剤、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、［７］記載の光重合開始剤以外の硬化触媒、［９］記載の有機無機ハイブリッド（メタ）アクリレート以外の金属酸化物微粒子、及び［１］記載の式（１）以外の紫外線吸収剤を含む群から選択された１以上の添加剤を更に含むことを特徴とする［６］〜［９］のいずれかに記載のコーティング組成物。
［１１］ 基材に直接又は少なくとも１種の他の層を介して［６］〜［１０］のいずれかに記載のコーティング組成物の硬化被膜を被覆してなる被覆物品。
［１２］ 基材が、有機樹脂又は木材である［１１］記載の被覆物品。 Therefore, this invention provides the following reactive ultraviolet absorber, its manufacturing method, coating composition, and a coated article.
[1] A reactive ultraviolet absorber represented by the following general formula (1).

{Wherein Y ¹ and Y ² are each independently a substituent of the general formula (2);

* Indicates a binding site, r is 0 or 1,
R ¹ , R ² and R ³ are each independently a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 4 to 12 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or 1 carbon atom. -20 alkoxy group, C4-C12 cycloalkoxy group, C2-C20 alkenyloxy group, C7-C20 aralkyl group, halogen atom, -C≡N, C1-C5 haloalkyl Group, —SO ₂ R ′, —SO ₃ H, —SO ₃ M (M = alkali metal), —COOR ′, —CONHR ′, —CONR′R ″, —OCOOR ′, —OCOR ′, —OCONHR ′, A (meth) acrylamino group, a (meth) acryloxy group, or an optionally substituted aryl group having 6 to 12 carbon atoms or a heteroaryl group having 3 to 12 carbon atoms,
R ′ and R ″ are a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 4 to 12 carbon atoms, an optionally substituted aryl group having 6 to 12 carbon atoms, or 3 to 12 carbon atoms. Represents a heteroaryl group,
X is a saturated hydrocarbon residue in which at least one of divalent to tetravalent linear or branched oxygen, nitrogen, sulfur and phosphorus atoms may be interposed;
T represents a urethane group —O— (C═O) —NH—,
Q is a saturated hydrocarbon residue in which at least one of a divalent or trivalent linear or branched oxygen, nitrogen, sulfur and phosphorus atom may be interposed;
P is a (meth) acryloxy group,
m is 1 or 2,
n is an integer of 1 to 3, but m and n are not 1 at the same time. }
[2] X is a group represented by the following general formula (3) or (4), and Q is a group represented by the following general formula (5) or (6) Reactive UV absorber.

{In the formula, * 1 is bonded to oxygen in the formula (1), * 2 is bonded to T in the formula (1), * 3 is independently a hydrogen atom, or It is bonded to T in the above formula (1) through a divalent saturated hydrocarbon group which may be directly or at least one of straight-chain or branched oxygen, nitrogen, sulfur and phosphorus atoms. , * 3 is bonded to T directly or through a divalent saturated hydrocarbon group in which at least one of straight-chain or branched oxygen, nitrogen, sulfur and phosphorus atoms may be interposed. Yes. }

{In the formula, * 4 is bonded to T in the formula (1), and * 5 is bonded to P in the formula (1). }
[3] In the formula (1), R ¹ , R ² and R ³ are each independently a hydrogen atom or a methyl group,
X is a group represented by the formula (3),
Q is a group represented by the formula (6),
m is 2,
n is 1, The reactive ultraviolet absorber as described in [2] characterized by the above-mentioned.
[4] The method for producing a reactive ultraviolet absorbent according to any one of [1] to [3], comprising the following step (II):
(II) a hydroxyl group bonded to X of the precursor compound represented by the following formula (7);

{Wherein Y ¹ , Y ² , X and n are the same as described above. }
The process with which the isocyanate group of the compound represented by following formula (8) is made to react.

{Wherein Q, P and m are the same as described above. }
[5] The method for producing a reactive ultraviolet absorbent according to [4], wherein the step (II) is performed after the following step (I).
(I) In the formula (1), when X is the formula (4) described in [2], an ester compound represented by the following formula (9);

{Wherein Y ¹ and Y ² are the same as defined above, and R ⁴ is a saturated hydrocarbon in which at least one of monovalent linear or branched oxygen, nitrogen, sulfur and phosphorus atoms may intervene. It is a group. }
A step of transesterifying a polyhydric alcohol compound represented by the following formula (10) to obtain a precursor compound of the formula (7).

{In the formula, R ⁵ , R ⁶ and R ⁷ are each independently a monovalent group in which at least one of a hydrogen atom, a hydroxyl group, a linear or branched oxygen, nitrogen, sulfur and phosphorus atom may intervene. A saturated hydrocarbon group, or a monovalent saturated hydrocarbon group in which a hydroxyl group is bonded to a terminal at which at least one of straight-chain or branched oxygen, nitrogen, sulfur and phosphorus atoms may intervene, and at least 1 One is a hydroxyl group or a saturated hydrocarbon group in which a hydroxyl group is bonded to a terminal which may be intervened with at least one of straight or branched oxygen, nitrogen, sulfur and phosphorus atoms. }
[6] A coating composition comprising the reactive ultraviolet absorbent according to any one of [1] to [3] and a binder precursor.
[7] The coating composition according to [6], wherein the binder precursor contains at least one monofunctional or polyfunctional (meth) acrylate, and further contains at least one photopolymerization initiator.
[8] The binder precursor includes one or more selected from the group consisting of a hydrolyzate or a hydrolyzed condensate of urethane poly (meth) acrylate and (meth) acryloyl group-containing alkoxysilane. 7] The coating composition according to the above.
[9] Furthermore, the binder precursor contains an organic-inorganic hybrid (meth) acrylate obtained by hydrolysis / condensation of colloidal silica and (meth) acrylic functional alkoxysilane [7] or [8] The coating composition according to [8].
[10] Antifouling agent, water repellent, leveling agent, colorant, pigment, adhesion promoter, infrared absorber, light stabilizer, curing catalyst other than the photopolymerization initiator described in [7], [9] It further comprises one or more additives selected from the group comprising metal oxide fine particles other than organic-inorganic hybrid (meth) acrylates and ultraviolet absorbers other than formula (1) described in [1]. [6] The coating composition according to any one of [9].
[11] A coated article obtained by coating a cured film of the coating composition according to any one of [6] to [10] directly or via at least one other layer on a substrate.
[12] The coated article according to [11], wherein the substrate is an organic resin or wood.

  ADVANTAGE OF THE INVENTION According to this invention, the novel benzotriazine type ultraviolet absorber which shows the outstanding ultraviolet absorptivity and has several (meth) acryl functional group is obtained easily. In addition, the coating composition containing the ultraviolet absorbent according to the present invention is excellent in scratch resistance due to a high degree of crosslinking density and long-term weather resistance due to being able to be stably held in the coating film without bleeding out the ultraviolet absorbent. .

It is the figure which showed the GPC chart of the compound and raw material which were obtained in Example 1 of this invention. Is a diagram showing the ¹ H-NMR chart of the compound obtained in Example 1 of the present invention. It is the figure which showed IR chart of the compound obtained in Example 1 of this invention. It is the figure which showed the transmission spectrum chart of the film obtained in Example 15 of this invention.

｛式中、Ｙ¹及びＹ²は互いに独立して、一般式（２）の置換基である。｝

Reactive ultraviolet absorber of the present invention The reactive ultraviolet absorber of the present invention is represented by the following general formula (1).

{Wherein Y ¹ and Y ² are each independently a substituent of the general formula (2). }

  Here, * indicates a binding site. r is 0 or 1, preferably 1. When r = 1, it is considered that the radical conjugated system generated upon absorption of ultraviolet rays spreads to stabilize the system.

R ¹ , R ² and R ³ are each independently a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 4 to 12 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or 1 carbon atom. -20 alkoxy group, C4-C12 cycloalkoxy group, C2-C20 alkenyloxy group, C7-C20 aralkyl group, halogen atom, -C≡N, C1-C5 haloalkyl Group, —SO ₂ R ′, —SO ₃ H, —SO ₃ M (M = alkali metal), —COOR ′, —CONHR ′, —CONR′R ″, —OCOOR ′, —OCOR ′, —OCONHR ′, A (meth) acrylamino group, a (meth) acryloxy group, or an aryl group having 6 to 12 carbon atoms or a heteroaryl group having 3 to 12 carbon atoms which may be substituted with a halogen atom, etc. Among them, hydrogen Atom, hydroxyl group, charcoal C 1 -C 20 alkyl group, an alkoxy group having 1 to 20 carbon atoms, a halogen atom, preferably an aryl group having 6 to 12 carbon atoms, a hydrogen atom, more preferably an alkyl group having 1 to 20 carbon atoms.

  R ′ and R ″ are a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 4 to 12 carbon atoms, or an aryl group having 6 to 12 carbon atoms which may be substituted with a halogen atom, or the like. A heteroaryl group having 3 to 12. Among them, a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and an aryl group having 6 to 12 carbon atoms are preferable, and a hydrogen atom and an alkyl group having 1 to 20 carbon atoms are more preferable. .

｛式中、＊１は前記式（１）中の酸素と結合しており、＊２は前記式（１）中のＴと結合しており、＊３は互いに独立して、水素原子、又は直接あるいは直鎖もしくは分岐の酸素、窒素、硫黄及びリン原子のうち少なくとも１種が介在していてもよい２価の飽和炭化水素基を介して上記式（１）中のＴと結合しており、＊３の少なくとも１つは直接あるいは直鎖もしくは分岐の酸素、窒素、硫黄及びリン原子のうち少なくとも１種が介在していてもよい２価の飽和炭化水素基を介してＴと結合している。｝ X is an alkyl group having 1 to 20 carbon atoms and a cycloalkyl group having 4 to 12 carbon atoms, in which at least one of divalent to tetravalent linear or branched oxygen, nitrogen, sulfur and phosphorus atoms may be interposed. Saturated hydrocarbon residues such as Among these, a group represented by the following general formula (3) or (4) is preferable from the viewpoint of ease of synthesis and availability of raw materials.

{In the formula, * 1 is bonded to oxygen in the formula (1), * 2 is bonded to T in the formula (1), * 3 is independently a hydrogen atom, or It is bonded to T in the above formula (1) through a divalent saturated hydrocarbon group which may be directly or at least one of straight-chain or branched oxygen, nitrogen, sulfur and phosphorus atoms. , * 3 is bonded to T directly or through a divalent saturated hydrocarbon group in which at least one of straight-chain or branched oxygen, nitrogen, sulfur and phosphorus atoms may be interposed. Yes. }

  T represents a urethane group —O— (C═O) —NH—.

｛式中、＊４は前記式（１）中のＴと結合しており、＊５は前記式（１）中のＰと結合している。｝ Q is an alkyl group having 1 to 20 carbon atoms and a cycloalkyl group having 4 to 12 carbon atoms, in which at least one of 2 to 3 valent linear or branched oxygen, nitrogen, sulfur and phosphorus atoms may be interposed. Saturated hydrocarbon residues such as Among these, a group represented by the following general formula (5) or (6) is preferable from the viewpoint of ease of synthesis and availability of raw materials.

{In the formula, * 4 is bonded to T in the formula (1), and * 5 is bonded to P in the formula (1). }

｛式中、Ｒ⁸は水素原子又はメチル基を示す。｝ P is a (meth) acryloxy group. Specifically, it is represented by the following general formula (11).

{Wherein R ⁸ represents a hydrogen atom or a methyl group. }

  m is 1 or 2, and n is an integer of 1 to 3, but m and n are not 1 at the same time. Preferably, m is 2 and n is 1.

As an example of the reactive ultraviolet absorber of the present invention, the availability of raw materials, compatibility with a relatively high binder precursor such as polyfunctional (meth) acrylate, and photocurability are excellent. The following compounds can be mentioned.

（１７）

(17)

Production Method of Reactive Ultraviolet Absorber of the Present Invention The production method of the reactive ultraviolet absorber of the present invention is not particularly limited. For example, it can be obtained by combining a general transesterification reaction or urethanization reaction. Among these, a preferable production method will be described below.

｛式中、Ｙ¹、Ｙ²、Ｘ、ｎは前記と同一である。｝ As a manufacturing method of the reactive ultraviolet absorber of the present invention, first, a precursor compound represented by the following formula (7) is prepared.

{Wherein Y ¹ , Y ² , X and n are the same as described above. }

｛式中、Ｙ¹、Ｙ²は前記と同じである。Ｒ⁴は１価の直鎖又は分岐の酸素、窒素、硫黄及びリン原子のうち少なくとも１種が介在していてもよい飽和炭化水素基である。｝

｛式中、Ｒ⁵、Ｒ⁶、Ｒ⁷は独立して、水素原子、水酸基、直鎖もしくは分岐の酸素、窒素、硫黄及びリン原子のうち少なくとも１種が介在していてもよい１価の飽和炭化水素基、又は直鎖もしくは分岐の酸素、窒素、硫黄及びリン原子のうち少なくとも１種が介在していてもよい末端に水酸基が結合した１価の飽和炭化水素基であって、少なくとも１つは水酸基又は直鎖もしくは分岐の酸素、窒素、硫黄及びリン原子のうち少なくとも１種が介在していてもよい末端に水酸基が結合した１価の飽和炭化水素基である。｝

｛式中、Ｙ¹、Ｙ²、ｎは前記と同一である。Ｘ’は式（４）で示される基等の２〜４価の直鎖又は分岐の酸素、窒素、硫黄及びリン原子のうちの少なくとも１種が介在していてもよいエステル基を含む飽和炭化水素残基である。｝ In this case, the precursor compound in which X contains an ester group (COO group) such as the above formula (4) is an ester compound represented by the following formula (9) and a polyhydric alcohol compound represented by the following formula (10). It is preferable to carry out a transesterification reaction to obtain a precursor compound of the following formula (7a).

{Wherein Y ¹ and Y ² are the same as described above. R ⁴ is a saturated hydrocarbon group in which at least one of monovalent linear or branched oxygen, nitrogen, sulfur and phosphorus atoms may be interposed. }

{In the formula, R ⁵ , R ⁶ and R ⁷ are each independently a monovalent group in which at least one of a hydrogen atom, a hydroxyl group, a linear or branched oxygen, nitrogen, sulfur and phosphorus atom may intervene. A saturated hydrocarbon group, or a monovalent saturated hydrocarbon group in which a hydroxyl group is bonded to a terminal at which at least one of straight-chain or branched oxygen, nitrogen, sulfur and phosphorus atoms may intervene, and at least 1 One is a monovalent saturated hydrocarbon group in which a hydroxyl group is bonded to a terminal which may have at least one of a hydroxyl group or a straight or branched oxygen, nitrogen, sulfur and phosphorus atom. }

{Wherein Y ¹ , Y ² and n are the same as described above. X ′ is a saturated carbonization containing an ester group in which at least one of a divalent to tetravalent linear or branched oxygen, nitrogen, sulfur and phosphorus atom such as a group represented by the formula (4) may be interposed It is a hydrogen residue. }

｛式中、Ｑ、Ｐ、ｍは前記と同一である。｝ Next, it is preferable to obtain the target compound of the formula (1) by the step (II): a step of reacting the precursor compound of the formula (7) with the isocyanate group of the compound represented by the following formula (8).

{Wherein Q, P and m are the same as described above. }

｛式中、Ｙ¹、Ｙ²は前記と同一であり、Ｒ⁴は１価の直鎖又は分岐の酸素、窒素、硫黄及びリン原子のうち少なくとも１種が介在していてもよい飽和炭化水素基である。｝
下記式（１０）で表される多価アルコール化合物とをエステル交換反応させて、下記式（７ａ）の前駆化合物を得る。

｛式中、Ｒ⁵、Ｒ⁶、Ｒ⁷は前記と同一である。｝

｛式中、Ｘ’は２〜４価の直鎖又は分岐の酸素、窒素、硫黄及びリン原子のうちの少なくとも１種が介在していてもよいエステル基を含む飽和炭化水素残基であり、特に式（４）の基である。Ｙ¹、Ｙ²、ｎは前記と同一である。｝ Step (I)
In the precursor compound of the formula (7), if it is a known compound such as when X is represented by the formula (3), it is prepared by a known method.
In the case where X contains an ester group (COO group) such as the one represented by the formula (4),
An ester compound represented by the following formula (9);

{Wherein Y ¹ and Y ² are the same as defined above, and R ⁴ is a saturated hydrocarbon in which at least one of monovalent linear or branched oxygen, nitrogen, sulfur and phosphorus atoms may intervene. It is a group. }
A precursor compound of the following formula (7a) is obtained by transesterification with a polyhydric alcohol compound represented by the following formula (10).

{Wherein R ⁵ , R ⁶ and R ⁷ are the same as described above. }

{In the formula, X ′ is a saturated hydrocarbon residue containing an ester group which may be intervened with at least one of divalent to tetravalent linear or branched oxygen, nitrogen, sulfur and phosphorus atoms; Particularly the group of formula (4). Y ¹ , Y ² and n are the same as described above. }

R ⁴ in the formula (9) is a saturated hydrocarbon group having 1 to 25 carbon atoms in which at least one of monovalent linear or branched oxygen, nitrogen, sulfur and phosphorus atoms may be interposed. is there. Specifically, methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, n-hexyl, iso-hexyl Cyclohexyl, n-heptyl, iso-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl and the like. Of these, n-octyl is preferred because of the availability of raw materials.

  As a commercial item of the compound represented by said Formula (9), brand name "Tinuvin479" (made by BASF Corporation) can be mentioned, for example.

Specifically, as R ⁵ , R ⁶ , and R ⁷ in the formula (10), at least one of hydrogen atom, hydroxyl group, linear or branched oxygen, nitrogen, sulfur, and phosphorus atoms is interposed. A monovalent saturated hydrocarbon group, or a monovalent saturated hydrocarbon group in which a hydroxyl group is bonded to a terminal at which at least one of straight-chain or branched oxygen, nitrogen, sulfur and phosphorus atoms may be interposed In this case, at least one is a hydroxyl group or a saturated hydrocarbon group in which a hydroxyl group is bonded to a terminal which may have at least one of straight-chain or branched oxygen, nitrogen, sulfur and phosphorus atoms. Of these, a methyl group, a hydroxyl group, and a methylol group are preferred from the viewpoint of availability of raw materials. Specific examples include pentaerythritol, trimethylolethane, trimethylolpropane, dimethylolpropane, dimethylolbutane, dimethylolpentane, diethylene glycol, and triethylene glycol. Of these, pentaerythritol and trimethylolpropane are preferred because of the availability of raw materials.

  X ′ in the formula (7a) is a saturated hydrocarbon residue in which at least one of a divalent to tetravalent linear or branched oxygen, nitrogen, sulfur and phosphorus atom may be interposed. Specifically, an ester-containing group containing a residue derived from the formula (10).

  The temperature at which the formula (9) and the formula (10) in this step (I) are reacted is preferably in the range of 10 to 200 ° C. More preferably, it is 20-180 degreeC, and when it is less than 10 degreeC, reaction time takes and it is unpreferable from a viewpoint of productivity. On the other hand, when the temperature exceeds 200 ° C., by-products due to side reactions tend to increase, and the products may be colored.

  A catalyst may be used for the reaction in the step (I). As the catalyst, it is preferable to use a known catalyst that is usually used in a transesterification reaction. For example, a tin-based catalyst corresponds to this. As a usage-amount, the range of 0-5% is preferable with respect to the whole quantity of the compound represented by the said Formula (9) and Formula (10), More preferably, it is 1,000 ppm-3%. When it exceeds 5%, a by-product is easily produced as a by-product, and the product is easily colored.

  The compounds represented by the formulas (9) and (10) are desirably reacted in equimolar amounts, but not limited thereto.

  A solvent may be used in the reaction of step (I). As the solvent, a solvent capable of dissolving the compound represented by the formula (9) and having no active hydrogen is preferable. Use of a solvent having active hydrogen is not preferable because by-products other than the precursor compound of the formula (7a) are generated. Further, for the purpose of removing water from the reaction system, azeotropic dehydration, molecular sieves, or the like may be performed. Furthermore, it is more preferable to use the solvent used at the time of preparation of a coating composition from a viewpoint that a coating composition can be prepared without removing a solvent from the reaction material of the following following process (II).

｛式中、Ｑは２〜３価の直鎖又は分岐の酸素、窒素、硫黄及びリン原子のうち少なくとも１種が介在していてもよい飽和炭化水素残基であり、Ｐは（メタ）アクリルオキシ基であり、ｍは１又は２である。｝ Step (II)
In the step (II), the hydroxyl group bonded to X in the precursor compound represented by the formula (7) is reacted with the isocyanate group of the compound represented by the following formula (8), whereby the formula ( This is a step of obtaining a reactive ultraviolet absorber represented by 1).

{In the formula, Q is a saturated hydrocarbon residue in which at least one of a bivalent or trivalent linear or branched oxygen, nitrogen, sulfur and phosphorus atom may intervene, and P is a (meth) acrylic. An oxy group, and m is 1 or 2; }

As Q in the formula (8), specifically, —CH ₂ —, —CH ₂ CH ₂ —, —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 And so on. Note that = indicates not a double bond but two bonds.

｛式中、＊４は前記式（１）中のＴと結合しており、＊５は前記式（１）中のＰと結合している。｝。 Particularly preferred examples are groups represented by the following formula (5) or (6).

{In the formula, * 4 is bonded to T in the formula (1), and * 5 is bonded to P in the formula (1). }.

｛式中、Ｒ⁸は水素原子又はメチル基を示す。｝ Specifically, P in the formula (8) is represented by the following general formula (11).

{Wherein R ⁸ represents a hydrogen atom or a methyl group. }

  M in the formula (8) is 1 or 2, and preferably 2. This is because when m exceeds 2, synthesis is difficult and difficult to obtain. Further, when n in the formula (1) is 1, m is not 1. In this case, in the formula (1), the obtained compound is a mono (meth) acryloxy body, so-called monofunctional, and cannot be three-dimensionally cross-linked. This is because it becomes prominent.

  Specific examples of the formula (8) include 2-acryloyloxyethyl isocyanate {trade name “Karenz AOI” (manufactured by Showa Denko KK)}, 1,1-bis (acryloyloxymethyl) ethyl isocyanate {trade name “Karenz BEI "(Made by Showa Denko KK)}, 2-methacryloyloxyethyl isocyanate {trade name" Karenz MOI "(made by Showa Denko KK)} and the like.

  In this step (II), the temperature at which the formula (7) and the formula (8) are reacted is preferably in the range of 10 to 200 ° C. More preferably, it is 20-180 degreeC, and when it is less than 10 degreeC, reaction time takes and it is unpreferable from a viewpoint of productivity. On the other hand, when the temperature exceeds 200 ° C., by-products due to side reactions tend to increase, and the products may be colored.

  A catalyst may be used for the reaction in the step (II). As the catalyst, it is preferable to use a known catalyst that is usually used in a urethanization reaction. For example, a tin-based catalyst corresponds to this. As a usage-amount, the range of 0-10,000 ppm is preferable with respect to the whole quantity of the compound represented by the said Formula (7) and Formula (8), More preferably, it is 100-5,000 ppm. When it exceeds 10,000 ppm, a by-product is easily produced as a by-product, and the product is easily colored.

  The compounds represented by the formulas (7) and (8) are desirably reacted in an equimolar amount, but not limited thereto. What is necessary is just to adjust with the number of the hydroxyl groups which can react with the isocyanate group in the said Formula (8) in the said Formula (7). However, it is preferable to adjust the ratio of the formulas (7) and (8) so that isocyanate groups do not remain in the reaction product. When the isocyanate group remains, the storage stability when the coating composition is formed tends to be lowered.

Here, in the formula (7), there is a hydroxyl group bonded to the benzene ring, but there is no urethanization reaction with the isocyanate group in the formula (8). The reason for this is considered to be that the reaction between the phenolic hydroxyl group and the isocyanate group is slow, and the area around the hydroxyl group is complicated by steric hindrance. Actually, protons of phenolic hydroxyl groups remain in ¹ H-NMR after the reaction.

  In the urethanization reaction, a polymerization inhibitor such as p-methoxyphenol may be used in order to suppress polymerization of the (meth) acryloxy group. Polymerization can also be suppressed by carrying out the reaction atmosphere in the air or under nitrogen containing 4% oxygen, and these may be used in combination.

  A solvent may be used in the reaction of step (II). As the solvent, a solvent capable of dissolving the compound represented by the formula (7) and having no active hydrogen is preferable. Use of a solvent having active hydrogen is not preferable because it reacts with the isocyanate group in the formula (8) to produce a by-product. Further, for the purpose of removing water from the reaction system, azeotropic dehydration, molecular sieves, or the like may be performed. Furthermore, from the viewpoint that the coating composition can be prepared without removing the solvent from the reaction product of step (II), it is more preferable to use the solvent used in the preparation of the coating composition.

  Here, the ratio of the ultraviolet absorbing group per molecular weight of one molecule of the ultraviolet absorber is defined as the ultraviolet absorbing group content.

Coating composition containing the reactive ultraviolet absorber of the present invention The coating composition of the present invention comprises the reactive ultraviolet absorber of the present invention and a binder precursor.

  Any binder precursor can be used as long as it can be a coating binder. For example, thermoplastic resins such as (meth) acrylic resins and polyurethane resins, and photocurable (meth) acrylic, monofunctional and / or polyfunctional epoxy compounds composed of monofunctional and / or polyfunctional (meth) acrylates. Examples thereof include a light or thermosetting epoxy type and a thermosetting silicone type using silanol. Among these, from the viewpoints of productivity and durability, a photocurable (meth) acrylic system composed of monofunctional and / or polyfunctional (meth) acrylate is preferable.

  As a photocurable (meth) acrylic coating composition using monofunctional and / or polyfunctional (meth) acrylate, specifically, the component (A) as the reactive ultraviolet absorber of the present invention, monofunctional and / or Or the (B) component which is polyfunctional (meth) acrylate, and a photoinitiator (C) component are included. Further, various additives may be added as other components as long as the effects of the present invention are not impaired.

  The content of the component (A) is preferably in the range of 1 to 100 parts by mass with respect to 100 parts by mass of the component (B). Even more preferably, it is 5 to 80 parts by mass. When the amount is less than 1 part by mass, the weather resistance of the resulting coated article cannot be sufficiently expressed, and when it exceeds 100 parts by mass, the scratch resistance and adhesion to the substrate of the resulting cured coating film are reduced. There is a risk.

  The component (B) is not particularly limited as long as it can be photocured. Usable are urethane (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, hydrolyzate / condensate of (meth) acryloyloxyalkoxysilane, colloidal silica and (meth) acryloyloxyalkoxysilane Monofunctional (meth) acrylates having polymerizable unsaturated bonds such as organic-inorganic hybrid (meth) acrylates obtained by hydrolytic condensation of polyfunctional (meth) acrylates, etc., depending on the required performance of the coating film May be selected as appropriate.

  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, Cyclodecane (meth) acrylate, polyethylene glycol mono (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, isobornyl (meth) acrylate , Mono (meth) acrylates such as allyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenyl (meth) acrylate, phthalic anhydride and 2-hydroxyethyl Examples include mono (meth) acrylate compounds such as adducts with (meth) acrylate.

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

  The (meth) acryloyloxyalkoxysilane hydrolyzate / condensate and the organic-inorganic hybrid (meth) acrylate obtained by hydrolytic condensation of colloidal silica and (meth) acryloyloxyalkoxysilane also have coating film hardness and durability. Used to improve Specifically, vinyltrimethoxysilane, vinyltriethoxysilane, p-styryltrimethoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 2- (meta ) Acryloxyethyltrimethoxysilane, 2- (meth) acryloxyethyltriethoxysilane, (meth) acryloxymethyltrimethoxysilane, (meth) acryloxymethyltriethoxysilane, 3- (meth) acryloxypropylmethyldi Single silane such as ethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 8- (meth) acryloxyoctyltrimethoxysilane, 8- (meth) acryloxyoctyltriethoxysilane, or a mixed silane with other silanes In some cases Hydrolyzate or hydrolysis condensate of (meth) acryloyl group-containing alkoxysilane obtained by (co) hydrolysis condensation in the presence of loyal silica, organic-inorganic hybrid vinyl compound, organic-inorganic hybrid (meth) acrylate compound, etc. Can be mentioned.

  These components (B) are preferably used in combination as needed. In particular, one or two types of polyfunctional (meth) acrylates, and urethane poly (meth) acrylate compounds having at least two or more radically polymerizable unsaturated double bonds in one molecule and (meth) acryloyl group-containing One or more combinations selected from hydrolysates or hydrolysis condensates of alkoxysilanes are suitable. Among them, hexanediol di (meth) acrylate, mono or polypentaerythritol poly (meth) acrylate, urethane poly (meth) acrylate having at least two radically polymerizable unsaturated double bonds in the molecule, and poly [ (Meth) acryloyloxyalkyl] (iso) cyanurate, (meth) acryloyloxypropylalkoxysilane alone or (co) hydrolyzate / condensate with other silanes, colloidal silica and (meth) acryloyloxypropylalkoxysilane, etc. Combination of (meth) acrylic functional alkoxysilane alone or organic inorganic hybrid (meth) acrylate obtained by (co) hydrolysis / condensation with other silane, heat resistance, chemical resistance, durability, substrate It is possible to obtain a coating film having excellent adhesion to the film.

  The component (C) may be appropriately selected from the viewpoints of compatibility and curability in the photocurable coating composition, and is not particularly limited.

  Specific examples of the component (C) include, for example, benzoin, benzoin monomethyl ether, benzoin isopropyl ether, acetoin, benzyl, benzophenone, p-methoxybenzophenone, diethoxyacetophenone, benzyldimethyl ketal, 2,2-diethoxyacetophenone, 1- Carbonyl compounds such as hydroxycyclohexyl phenyl ketone, methylphenylglyoxylate, 2-hydroxy-2-methyl-1-phenylpropan-1-one; sulfur compounds such as tetramethylthiuram monosulfide, tetramethylthiuram disulfide; 2,4 , 6-Trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylethoxyphosphine oxide, bis (2,4,6-trimethyl) Phosphoric acid compounds such as benzoyl) -phenylphosphine oxide and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide; 2-benzyl-2-dimethylamino-1- (4- Morpholinophenyl) butanone-1, camphorquinone and the like. These may be used individually by 1 type, or may be used in combination of 2 or more types, and can be combined arbitrarily according to the required coating film performance.

  The content of the component (C) is preferably in the range of 0.1 to 10 parts by mass with respect to 100 parts by mass in total of the components (A) and (B). Even more preferably, it is 1 to 8 parts by mass. If the amount is less than 0.1 parts by mass, the curing rate of the resulting coating film is remarkably reduced, and the scratch resistance and adhesion to the substrate may be reduced. On the other hand, when it exceeds 10 mass parts, coloring of a cured coating film and a fall of a weather resistance may arise.

  The coating composition containing the reactive ultraviolet absorbent [component (A)] of the present invention is optionally coated with an ultraviolet absorbent other than the component (A), an organic solvent, an antifouling agent, a water repellent, a leveling agent, Colorants, pigments, antioxidants, yellowing inhibitors, bluing agents, antifoaming agents, thickeners, antisettling agents, antistatic agents, surfactants, adhesion promoters, infrared absorbers, light stabilizers, Various additive components such as a curing catalyst and metal oxide fine particles may be contained. In particular, an antifouling agent, a water repellent, a leveling agent, a colorant, a pigment, an adhesion promoter, an infrared absorber, a light stabilizer, a curing catalyst other than the polymerization initiator, the organic-inorganic hybrid (meth) acrylate [hereinafter, One or more additives selected from the group comprising metal oxide fine particles other than (may be referred to as colloidal silica surface-treated with (meth) acryl-functional alkoxysilane] and ultraviolet absorbers other than component (A) Can further be included.

  The organic solvent is preferably selected according to the coating method. That is, when used for spray coating, alcohol solvents such as isobutanol, glycol solvents such as propylene glycol monomethyl ether, ester solvents typified by n-butyl acetate, ketone systems typified by methyl isobutyl ketone It is desirable that the viscosity of the coating composition be 20 mPa · s or less by arbitrarily combining a solvent and an aromatic solvent typified by toluene. Further, when used for painting by shower flow coating or dip, it is desirable that the viscosity of the coating composition is 100 mPa · s or less. On the other hand, in the case of a high solid type coating composition having a solid content exceeding 80% by mass, it is important to appropriately select a solvent in consideration of the solubility of various additives.

  The thickness of the coating composition of the coating composition of the present invention is not particularly limited, but is preferably 0.1 to 50 μm, and the hardness of the coating film, scratch resistance, long-term stable adhesion, and cracks are generated. In order to satisfy what is difficult to do, it is more preferable that it is 1-30 micrometers. If the thickness is less than 0.1 μm, the coating film may be easily damaged or may not be provided with sufficient ultraviolet absorbing ability, and if it exceeds 50 μm, the coating film may be easily cracked.

  Here, examples of the substrate to be used include organic resins such as plastic moldings, wood products, fibers, ceramics, glass, metals, and composites thereof. Suitable for use in materials, especially polycarbonate resin, polystyrene resin, acrylic resin, modified acrylic resin, urethane resin, thiourethane resin, polycondensate of halogenated bisphenol A and ethylene glycol, acrylic urethane resin, halogenated aryl group-containing acrylic Resins, sulfur-containing resins, polyalkylene terephthalate resins, cellulose resins, amorphous polyolefin resins, and the like, and composite resins thereof are preferable. Further, the surface of these resin base materials is treated, specifically, chemical conversion treatment, corona discharge treatment, flame treatment, plasma treatment, treatment with an acid or an alkaline solution, and the base body and the surface layer are different types. A laminate formed of a resin can also be used. Examples of laminates include laminates in which an acrylic resin layer or urethane resin layer is present on the surface layer of a polycarbonate resin substrate manufactured by a coextrusion method or a laminate method, or an acrylic resin layer is present in the surface layer of a polyester resin substrate. And the like.

  In addition, it can also be formed on the surface of the substrate directly or as necessary 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, etc. during coating. .

  Further, if necessary, on the surface of the cured coating film of the coating composition of the present invention, an adhesive 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, a water / oil repellent layer. Other coating layers such as a hydrophilic antifouling layer may be formed.

  The cured coating film of the coating composition of the present invention is excellent in scratch resistance, but an inorganic vapor deposition film layer may be coated on this coating film in order to obtain another level of scratch resistance. The inorganic vapor deposition film layer is not particularly limited as long as it is formed by a dry film forming method. For example, Si, Ti, Zn, Al, Ga, In, Ce, Bi, Sb, B, Zr And a layer mainly composed of at least one or more kinds of metals or metal oxides, nitrides, sulfides, and the like having elements such as Sn, Sn, and Ta. In addition, for example, a diamond-like carbon film layer having high hardness and excellent insulating properties can be used. The method for laminating the inorganic vapor deposition film layer is not particularly limited as long as it is a dry film formation method. For example, physical vapor deposition such as resistance heating vapor deposition, electron beam vapor deposition, molecular beam epitaxy, ion beam deposition, ion plating, sputtering, etc. Examples thereof include a phase growth method and a dry film forming method such as a chemical vapor deposition method such as thermal CVD, plasma CVD, photo CVD, epitaxial CVD, atomic layer CVD, and catCVD.

  The coated article coated with the cured product of the coating composition of the present invention thus obtained can be excellent in scratch resistance, ultraviolet absorption, heat resistance, water resistance and bleed-out resistance.

  The coating composition containing the reactive ultraviolet absorbent [component (A)] of the present invention is applied to a substrate and then cured by heating and / or light. From the viewpoint of productivity, a photo-curing coating is preferred. When curing by light irradiation, the coating composition is applied on the substrate so as to form a specified film thickness, and then the solvent is volatilized, and then a high-pressure mercury lamp, metal halide lamp, LED lamp, etc. are used. Irradiate ultraviolet rays or electron beams. The atmosphere for irradiation may be air or an inert gas such as nitrogen or argon.

Here, as a coating method, it can be coated on a substrate by a normal coating method, for example, various types such as brush coating, spraying, dipping, flow coating, roll coating, curtain coating, spin coating, knife coating, etc. A coating method can be selected.
After applying the coating composition, drying may be performed as necessary. Drying is not particularly limited as long as the conditions allow the solvent to be removed. For example, it is common to heat at a temperature lower than the heat resistance temperature of the substrate. Specifically, it can be heated at a temperature of 15 to 120 ° C. for 1 to 20 minutes.
Curing of the coating composition is preferably performed by light irradiation. Here, the irradiation source and the irradiation amount are not particularly limited. Specific examples of the irradiation source include low-pressure, medium-pressure, high-pressure, and ultra-high-pressure mercury lamps, chemical lamps, carbon arc lamps, xenon lamps, metal halide lamps, fluorescent lamps, tungsten lamps, and sunlight. The irradiation dose is preferably 100~10000mJ / cm ^2, more preferably include a range of 300~5000mJ / cm ^2.

  The reactive ultraviolet absorber of the present invention is desirably used as a photocurable coating composition used particularly outdoors. The photocurable coating composition is mainly applied to the surface of automobile headlamp lenses, vehicle sensors, and resin glass. These substrates are polycarbonates, and polycarbonates are usually used because they have high impact resistance, heat resistance, transparency and lightness. However, since the polycarbonate has insufficient performance such as chemical resistance, weather resistance, and scratch resistance, it is desirable to use the coating composition of the present invention.

  In addition, the polycarbonate coated with the coating composition of the present invention prevents yellowing and surface deterioration of the polycarbonate, has a surface hardness equivalent to that of glass, is lightweight, and has easy moldability. , Vehicle sensors, vehicle windows, outdoor signboards, glass windows in greenhouses and outdoor buildings, roofs of terraces and garages, balconies, instrument covers, etc.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to these Examples. In the following examples, “part” and “%” mean “part by mass” and “% by mass”, respectively, unless otherwise specified. Moreover, a weight average molecular weight is a weight average molecular weight of polystyrene conversion by gel permeation chromatography (GPC).

GPC measurement condition device: HLC-8320GPC manufactured by Tosoh Corporation
Column: Tosoh Corporation TSKgel G4000HXL + G3000HXL + G2000HXL + G2000HXL (each inner diameter 6 mm, length 150 mm)
Developing solution: tetrahydrofuran column temperature: 40 ° C
Flow rate: 1 mL / min
Detector: Refractive index (RI)
Standard: Monodisperse polystyrene

Proton nuclear magnetic resonance spectrum ( ¹ H-NMR) measurement condition apparatus: AVANCE III 400 manufactured by BRUKER
Solvent: CDCl ₃
Internal standard: Tetramethylsilane (TMS)

Infrared absorption spectrum (IR) measurement condition apparatus: Nicolet 6700 manufactured by Thermo Fisher

<Synthesis of reactive UV absorber>
[Example 1]
To a 1 L flask, Tinuvin 405 (manufactured by BASF; 2- [4-[(2-hydroxy-3- (2′-ethyl) hexyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4 -Dimethylphenyl) -1,3,5-triazine) 87.6 g (0.15 mol), propylene glycol monomethyl ether acetate 391.5 g, and methoxyphenol 0.12 g were charged in a 4% oxygen / nitrogen atmosphere. The mixture was heated and stirred at 80 ° C. Next, 35.9 g (0.15 mol) of Karenz BEI (manufactured by Showa Denko KK; 1,1-bis (acryloyloxymethyl) ethyl isocyanate) and 0.12 g of dioctyltin oxide were added and reacted at 80 ° C. for 5 hours. I let you. After cooling to room temperature, the solution was passed through a column filled with silica gel and concentrated under reduced pressure to obtain 110.8 g of a yellow transparent viscous liquid. This liquid was a compound (S1) represented by the following formula (12) from the results of GPC (FIG. 1), ¹ H-NMR (FIG. 2) and IR (FIG. 3). Moreover, the ultraviolet absorptive group content rate of S1 calculated from following formula (12) is 48%.

[Example 2]
To a 1 L flask, Tinuvin 400 (manufactured by BASF; 2- [4-{(hydroxy-3-dodecyloxypropyl) oxy} -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1 , 3,5-triazine) (active ingredient 85%, solid content conversion 0.15 mol) was charged and concentrated under reduced pressure to remove volatile components. After cooling to room temperature, 391.5 g of propylene glycol monomethyl ether acetate and 0.12 g of methoxyphenol were charged, and the mixture was heated and stirred at 80 ° C. in a 4% oxygen / nitrogen atmosphere. Next, 35.9 g (0.15 mol) of Karenz BEI (manufactured by Showa Denko KK; 1,1-bis (acryloyloxymethyl) ethyl isocyanate) and 0.12 g of dioctyltin oxide were added and reacted at 80 ° C. for 5 hours. I let you. After cooling to room temperature, the solution was passed through a column filled with silica gel and concentrated under reduced pressure to obtain 120.3 g of a compound (S2) represented by the following formula (13). Moreover, the ultraviolet absorptive group content rate of S2 calculated from following formula (13) is 44%.

[Example 3]
To a 1 L flask, Tinuvin 479 (manufactured by BASF; 2- [2-hydroxy-4- (1-octyloxycarbonylethoxy) phenyl] -4,6-bis (4-phenylphenyl) -1,3,5-triazine ) 101.7 g (0.15 mol), 1,1,1-tris (hydroxymethyl) propane 220 g, and dioctyltin oxide 8 g were charged and heated and stirred at 165 ° C. for 5 hours in a nitrogen atmosphere. Next, after cooling to room temperature, crystals were precipitated using methanol and filtered, and the crystals were washed with methanol. Then, the precursor compound shown by following formula (20) was obtained by making it recrystallize from toluene.

Next, 35 g (0.05 mol) of the precursor compound of the formula (20), 130.5 g of propylene glycol monomethyl ether acetate and 0.04 g of methoxyphenol were charged into a 500 mL flask at 80 ° C. in a 4% oxygen / nitrogen atmosphere. And stirred with heating. Next, 24 g (0.1 mol) of Karenz BEI (manufactured by Showa Denko KK; 1,1-bis (acryloyloxymethyl) ethyl isocyanate) and 0.04 g of dioctyltin oxide were added and reacted at 80 ° C. for 5 hours. . After cooling to room temperature, the solution was passed through a column packed with silica gel and concentrated under reduced pressure to obtain 41.8 g of a compound (S3) represented by the following formula (15). Moreover, the ultraviolet absorptive group content rate of S3 calculated from following formula (15) is 41%.

[Example 4]
To a 1 L flask, Tinuvin 479 (manufactured by BASF; 2- [2-hydroxy-4- (1-octyloxycarbonylethoxyphenyl] -4,6-bis (4-phenylphenyl) -1,3,5-triazine) 101.7 g (0.15 mol), 1,3-dimethyl-3,4,5,6-tetrahydro-2-pyrimidinone 250 g, pentaerythritol 250 g, and dioctyltin oxide 8 g were charged to 165 ° C. in a nitrogen atmosphere. After cooling to room temperature, crystals were precipitated using methanol and filtered, and the crystals were washed with methanol, and then recrystallized from toluene to obtain the following formula (21). A precursor compound was obtained.

Next, 35 g (0.05 mol) of the precursor compound of the formula (21) and 130.5 g of propylene glycol monomethyl ether acetate and 0.04 g of methoxyphenol were charged into a 500 mL flask at 80 ° C. in a 4% oxygen / nitrogen atmosphere. And stirred with heating. Subsequently, 21.3 g (0.15 mol) of Karenz AOI (manufactured by Showa Denko KK; 2-acryloyloxyethyl isocyanate) and 0.04 g of dioctyltin oxide were added and reacted at 80 ° C. for 5 hours. After cooling to room temperature, the solution was passed through a column packed with silica gel and concentrated under reduced pressure to obtain 39.1 g of a compound (S4) represented by the following formula (19). Moreover, the ultraviolet absorptive group content rate of S4 calculated from following formula (19) is 43%.

<Synthesis of other UV absorbers>
[Reference Example 1 (UV absorber having one methacryloxy group)]
To a 500 mL flask, Tinuvin 405 (manufactured by BASF; 2- [4-[(2-hydroxy-3- (2′-ethyl) hexyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4 -Dimethylphenyl) -1,3,5-triazine) (29.2 g, 0.05 mol), propylene glycol monomethyl ether acetate (130 g), and methoxyphenol (0.04 g) were charged at 80 ° C. in a 4% oxygen / nitrogen atmosphere. The mixture was stirred with heating. Subsequently, 7.8 g (0.05 mol) of Karenz MOI (trade name, manufactured by Showa Denko KK, 2-methacryloyloxyethyl isocyanate) and 0.04 g of dioctyltin oxide were added and reacted at 80 ° C. for 5 hours. After cooling to room temperature, the solution was passed through a column filled with silica gel and concentrated under reduced pressure to obtain 34.3 g of a compound represented by the following formula (22) (T405MOI). Moreover, the ultraviolet absorptive group content rate of T405MOI calculated from the following formula (22) is 53%.

[Reference Example 2 (polymer having ultraviolet absorbing group and acryloxy group)]
By the method described in Example 1 of JP 2012-31434 A, a polymer having an ultraviolet absorbing group and an acryloxy group (PolUVA, nonvolatile content 40%) was obtained. Moreover, the ultraviolet absorptive group content rate of PolUVA is 16%.

[Reference Example 3 (silsesquioxane having an ultraviolet absorbing group and an acryloxy group)]
Silsesquioxane (SiUVA-1, non-volatile content 50%) having an ultraviolet absorbing group and an acryloxy group was obtained by the method described in Example 1 of JP2012-219102A. Moreover, the ultraviolet absorptive group content rate of SiUVA-1 is 16%.

[Reference Example 4 (UV absorber having alkoxysilyl group)]
The ultraviolet absorber (SiUVA-2) which has an alkoxy silyl group was obtained by the method of the synthesis example 3 of Unexamined-Japanese-Patent No. 2010-1111715. Moreover, the ultraviolet absorptive group content rate of SiUVA-2 is 55%.

[Reference Example 5 (Acrylic Silane Hydrolysis Condensate)]
Contains 142 parts of KBM5103 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., acryloyloxypropyltrimethoxysilane), 500 parts of isopropyl alcohol, 0.1 part of methoquinone, 1.0 part of tetramethylammonium hydroxide, and 20 parts of deionized water. The mixture was reacted at 20 ° C. for 24 hours to obtain a colorless and transparent liquid. Concentration by distillation under reduced pressure gave an acrylic silane hydrolysis condensate (5103SQ) which is a colorless and transparent liquid. The nonvolatile content was 99.3% and the weight average molecular weight was 1,900.

[Reference Example 6 (Organic inorganic hybrid acrylate; colloidal silica surface-treated with acrylic silane)]
KBM5103 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., acryloyloxypropyltrimethoxysilane) 2.8 parts, methyl ethyl ketone silica sol MEK-ST (trade name, manufactured by Nissan Chemical Industries, Ltd., number average particle size 45 nm, silica concentration 30%) 95 .6 parts (solid content: 27.4 parts) and ion-exchanged water (0.1 parts) were stirred at 80 ° C. for 3 hours, 1.4 parts of orthoformate methyl ester was added, and the mixture was further kept at the same temperature for 1 hour. A surface-treated silica particle dispersion was obtained by heating and stirring. The solid content was determined to be 32% by mass. The average particle diameter of the silica particles was 45 nm.

<Preparation of coating composition>
[Example 5]
1.33 parts of the compound (S1) obtained in Example 1, 21.1 parts of Aronix M403 (manufactured by Toagosei Co., Ltd., dipentaerythritol penta and hexaacrylate), HDDA (manufactured by Daicel Cytec Co., Ltd., 1,6-hexanediol) 3.9 parts diacrylate), IRGACURE 184 (BASF polymerization initiator, 1-hydroxycyclohexyl phenyl ketone) 0.45 parts, LUCILIN TPO (BASF polymerization initiator, 2,4,6-trimethylbenzoyldiphenylphosphine) Oxide) 0.45 parts, 0.17 part of KP341 (manufactured by Shin-Etsu Chemical Co., Ltd., polyether-modified silicone) and 30 parts of propylene glycol monomethyl ether as a leveling agent were blended to prepare a photocurable coating composition (C1). .

[Examples 6 to 10, Comparative Examples 1 to 11]
Using the compounds of Examples 1 to 4, the compounds of Reference Examples and other ultraviolet absorbers, the coating compositions (C2 to C6) and the comparisons in the same manner as in Example 5 with the formulations shown in Tables 1 and 2 The coating compositions (R1-R11) of Examples 1-11 were prepared. These coating compositions were applied to the surface of a polycarbonate NF-2000 sheet (thickness 5 mm × length 15 cm × width 10 cm) manufactured by Mitsubishi Engineering Plastics Co., Ltd. by flow coating, air-dried for 5 minutes, and heated at 80 ° C. for 1 minute. Thereafter, the coating film was cured by irradiating light with an irradiation amount of 600 mJ / cm ² using a high-pressure mercury lamp to obtain a test piece.

[Examples 11 to 14]
Using the ultraviolet absorbers of Examples 1 to 4, coating compositions (C7 to C10) were prepared in the same manner as in Example 5 with the formulations shown in Table 1. These coating compositions were applied to the surface of a polycarbonate NF-2000 sheet (thickness 5 mm × length 15 cm × width 10 cm) manufactured by Mitsubishi Engineering Plastics Co., Ltd. by flow coating, air-dried for 5 minutes, and heated at 80 ° C. for 1 minute. Thereafter, the coating film was cured by irradiating light with 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, and the results are shown in Table 1.

［ ］内の数字は、紫外線吸収性基含有率を示す。

The numbers in [] indicate the UV absorbing group content.

［ ］内の数字は、紫外線吸収性基含有率を示す。
（ ）内の数字は、固形分換算値を示す。

The numbers in [] indicate the UV absorbing group content.
Numbers in parentheses indicate solid content converted values.

  The coating films of Examples 5 to 8 (C1 to C4) maintained the same level of scratch resistance and improved weather resistance as compared with Comparative Example 10 (R10) containing no UV absorber. In Examples 9 to 14 (C5 to 10) in which the amount of the reactive ultraviolet absorbent of the present invention was increased, the weather resistance was further improved while maintaining the scratch resistance as compared with R10. Moreover, Example 13 (C9) and 14 (C10) which mix | blended the acryloyl group containing alkoxysilane hydrolysis-condensation product (5103SQ) have improved abrasion resistance compared with Example 9 (C5) which is not mix | blended. It was. On the other hand, in Comparative Example 2 (R2) and Comparative Example 3 (R3) using an ultraviolet absorber containing no reactive group, although the weather resistance was improved as compared with R10, the scratch resistance was reduced. . However, the weather resistance was slightly inferior to C1 to C4 of the present invention. This is presumably because the ultraviolet absorber is not incorporated in the binder. Further, in Comparative Example 1 (R1) and Comparative Example 4 (R4) using an ultraviolet absorber having one reactive group, scratch resistance and weather resistance were lowered as compared with C1. The same result was obtained for the polymer type ultraviolet absorber [Comparative Example 5 (R5)] and the ultraviolet absorbing silsesquioxane [Comparative Example 6 (R6)]. Furthermore, in Comparative Example 7 (R7), Comparative Example 8 (R8), and Comparative Example 9 (R9) in which the amount of these ultraviolet absorbers was increased, an abnormality in whitening of the coating film was observed, and the scratch resistance was greatly reduced. Was. Furthermore, in Comparative Example 11 (R11) to which an ultraviolet absorber having an alkoxysilyl group was added, the film was colored yellow, and the scratch resistance and weather resistance were inferior compared with Examples 9 and 10 (C5 and C6). It was. From these results, the effect of the reactive ultraviolet absorbent of the present invention is clear.

Abbreviations in Table 1 and Table 2 are as follows.
(B) Component A-M403: Aronix M403 (trade name, manufactured by Toagosei Co., Ltd., dipentaerythritol penta and hexaacrylate)
HDDA: HDDA (trade name, manufactured by Daicel Cytec, 1,6-hexanediol diacrylate)
U-4HA: Urethane acrylate U-4HA (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd., non-yellowing type)
5103SQ: Hydrolysis condensate of KBM5103 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., 3-acryloxypropyltrimethoxysilane) Silica: Organic inorganic hybrid acrylate dispersion [KBM5103 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., acryloyloxypropyl) Silica particle dispersion surface-treated with trimethoxysilane)
(C) Component I184: IRGACURE184 (trade name, manufactured by BASF, 1-hydroxycyclohexyl phenyl ketone)
L-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)
Solvent PGM: Propylene glycol monomethyl ether
Other UV absorber R93: RUVA-93 (trade name, manufactured by Otsuka Chemical Co., Ltd., 2- (2′-hydroxy-5′-methacryloxyethylphenyl) -2H-benzotriazole), calculated UV absorbing group-containing The rate is 65%.
T405: Tinuvin405 (trade name, manufactured by BASF, 2- [4-[(2-hydroxy-3- (2′-ethyl) hexyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4 -Dimethylphenyl) -1,3,5-triazine), the calculated UV-absorbing group content is 67%.
T479: Tinuvin479 (trade name, manufactured by BASF, 2- [2-hydroxy-4- (1-octyloxycarbonylethoxy) phenyl] -4,6-bis (4-phenylphenyl) -1,3,5-triazine ), The calculated UV-absorbing group content is 72%.
T405MOI: Addition reaction product of Tinuvin405 described in Reference Example 1 and Karenz MOI (trade name, Showa Denko KK, 2-methacryloyloxyethyl isocyanate) PolUVA: UV absorbing group and acryloxy group described in Reference Example 2 Polymer SiUVA-1 having: UV-absorbing group described in Reference Example 3 and silsesquioxane having an acryloxy group SiUVA-2: UV-absorbing agent having alkoxysilyl group described in Reference Example 4

Evaluation method of cured film <Appearance of coated film>
The coating film was visually observed to determine the presence or absence of abnormality.
○: No abnormality △: Colored ×: Foreign matter, unevenness, whitening abnormality

<Abrasion resistance>
In accordance with ASTM 1044, a wear wheel CS-10F was attached with a Taber abrasion tester, and the haze after 500 rotations under a load of 500 g was measured, and the difference in haze after the test and before the test was defined as scratch resistance.

<Initial adhesion>
In accordance with JIS K5400, using a razor blade, 25 vertical grids were made at intervals of 2 mm at intervals of 2 mm to produce 25 grids, and cello tape (registered trademark, manufactured by Nichiban Co., Ltd.) was adhered well. After that, when the film was peeled off in a 90 ° front direction, the number of squares (X) remaining without peeling off the coating film was indicated by X / 25.

<Boiling adhesion>
The adhesion after the evaluation sample was immersed in boiling water for 2 hours was evaluated in the same manner as the initial adhesion.

<Weather resistance evaluation>
Using I-Super UV Tester W-151 manufactured by Iwasaki Electric Co., Ltd., [Black panel temperature 63 ° C, humidity 50% RH, illuminance 50 mW / cm ² , rain 10 seconds / 1 hour 5 hours] → [Black panel temperature The test was conducted for 100 hours, 200 hours, and 300 hours under the conditions of repeating this cycle, with 1 cycle at 30 ° C. and 95% RH as one cycle. The state of the coating after the weather resistance test was observed visually or with a microscope (250 times magnification), and evaluated according to the following criteria.
○: No abnormality △: Slightly cracked or partially peeled ×: Cracked or entirely peeled on the entire coating film

[Example 15]
Using the coating composition (C1, R10) of Example 5 and Comparative Example 10, it was applied to a quartz glass plate (thickness 1 mm × length 4 cm × width 1 cm) by a flow coating method, air-dried for 5 minutes, and then a high pressure mercury lamp was used. The coating film was cured by light irradiation at an irradiation dose of 600 mJ / cm ² . When the transmission spectrum was measured with respect to the obtained film, as shown in FIG. 4, the film obtained from the coating composition C1 absorbed ultraviolet rays in a wavelength region of 300 nm or more, while obtained from the coating composition R10. It is clear that the obtained coating cannot absorb ultraviolet rays of 300 nm or more.

  The film obtained from the coating composition containing the reactive ultraviolet absorbent of the present invention has a significantly increased ultraviolet absorption, so that the deterioration of the polycarbonate resin as the substrate is greatly suppressed, and abnormalities after the weather resistance test are observed. It was possible to suppress the expression, and particularly the peel resistance was greatly improved.

Claims (12)

The reactive ultraviolet absorber represented by following General formula (1).

{Wherein Y ¹ and Y ² are each independently a substituent of the general formula (2);

* Indicates a binding site, r is 0 or 1,
R ¹ , R ² and R ³ are each independently a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 4 to 12 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or 1 carbon atom. -20 alkoxy group, C4-C12 cycloalkoxy group, C2-C20 alkenyloxy group, C7-C20 aralkyl group, halogen atom, -C≡N, C1-C5 haloalkyl Group, —SO ₂ R ′, —SO ₃ H, —SO ₃ M (M = alkali metal), —COOR ′, —CONHR ′, —CONR′R ″, —OCOOR ′, —OCOR ′, —OCONHR ′, A (meth) acrylamino group, a (meth) acryloxy group, or an optionally substituted aryl group having 6 to 12 carbon atoms or a heteroaryl group having 3 to 12 carbon atoms,
R ′ and R ″ are a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 4 to 12 carbon atoms, an optionally substituted aryl group having 6 to 12 carbon atoms, or 3 to 12 carbon atoms. Represents a heteroaryl group,
X is a saturated hydrocarbon residue in which at least one of divalent to tetravalent linear or branched oxygen, nitrogen, sulfur and phosphorus atoms may be interposed;
T represents a urethane group —O— (C═O) —NH—,
Q is a saturated hydrocarbon residue in which at least one of a divalent or trivalent linear or branched oxygen, nitrogen, sulfur and phosphorus atom may be interposed;
P is a (meth) acryloxy group,
m is 1 or 2,
n is an integer of 1 to 3, but m and n are not 1 at the same time. } The reactive ultraviolet ray according to claim 1, wherein X is a group represented by the following general formula (3) or (4), and Q is a group represented by the following general formula (5) or (6). Absorbent.

{In the formula, * 1 is bonded to oxygen in the formula (1), * 2 is bonded to T in the formula (1), * 3 is independently a hydrogen atom, or It is bonded to T in the above formula (1) through a divalent saturated hydrocarbon group which may be directly or at least one of straight-chain or branched oxygen, nitrogen, sulfur and phosphorus atoms. , * 3 is bonded to T directly or through a divalent saturated hydrocarbon group in which at least one of straight-chain or branched oxygen, nitrogen, sulfur and phosphorus atoms may be interposed. Yes. }

{In the formula, * 4 is bonded to T in the formula (1), and * 5 is bonded to P in the formula (1). } In the formula (1), R ¹ , R ² and R ³ are each independently a hydrogen atom or a methyl group,
X is a group represented by the formula (3),
Q is a group represented by the formula (6),
m is 2,
3. The reactive ultraviolet absorber according to claim 2, wherein n is 1. The method for producing a reactive ultraviolet absorbent according to any one of claims 1 to 3, comprising the following step (II).
(II) a hydroxyl group bonded to X of the precursor compound represented by the following formula (7);

{Wherein Y ¹ , Y ² , X and n are the same as described above. }
The process with which the isocyanate group of the compound represented by following formula (8) is made to react.

{Wherein Q, P and m are the same as described above. } The method for producing a reactive ultraviolet absorbent according to claim 4, wherein the step (II) is performed after the following step (I).
(I) In the formula (1), when X is the formula (4) according to claim 2, an ester compound represented by the following formula (9);

{Wherein Y ¹ and Y ² are the same as defined above, and R ⁴ is a saturated hydrocarbon in which at least one of monovalent linear or branched oxygen, nitrogen, sulfur and phosphorus atoms may intervene. It is a group. }
A step of transesterifying a polyhydric alcohol compound represented by the following formula (10) to obtain a precursor compound of the formula (7).

{In the formula, R ⁵ , R ⁶ and R ⁷ are each independently a monovalent group in which at least one of a hydrogen atom, a hydroxyl group, a linear or branched oxygen, nitrogen, sulfur and phosphorus atom may intervene. A saturated hydrocarbon group, or a monovalent saturated hydrocarbon group in which a hydroxyl group is bonded to a terminal at which at least one of straight-chain or branched oxygen, nitrogen, sulfur and phosphorus atoms may intervene, and at least 1 One is a hydroxyl group or a saturated hydrocarbon group in which a hydroxyl group is bonded to a terminal which may be intervened with at least one of straight or branched oxygen, nitrogen, sulfur and phosphorus atoms. }   A coating composition comprising the reactive ultraviolet absorber according to any one of claims 1 to 3 and a binder precursor.   The coating composition according to claim 6, wherein the binder precursor contains at least one monofunctional or polyfunctional (meth) acrylate, and further contains at least one photopolymerization initiator.   The said binder precursor contains 1 or more types selected from the group which consists of a hydrolyzate or hydrolysis-condensation product of urethane poly (meth) acrylate and (meth) acryloyl group containing alkoxysilane. Coating composition.   Furthermore, the said binder precursor contains the organic inorganic hybrid (meth) acrylate obtained by hydrolyzing and condensing colloidal silica and (meth) acryl functional alkoxysilane, The Claim 7 or 8 characterized by the above-mentioned. Coating composition.   Antifouling agent, water repellent, leveling agent, colorant, pigment, adhesion promoter, infrared absorber, light stabilizer, curing catalyst other than the photopolymerization initiator according to claim 7, and organic-inorganic hybrid according to claim 9. The metal oxide fine particles other than (meth) acrylate and one or more additives selected from the group comprising ultraviolet absorbers other than the formula (1) according to claim 1 are further included. 10. The coating composition according to any one of 9 above.   A coated article obtained by coating a cured film of the coating composition according to any one of claims 6 to 10 on a substrate directly or via at least one other layer.   The coated article according to claim 11, wherein the substrate is an organic resin or wood.

Images