JP2008189774A - Coating composition with good touch - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a coating composition having good touch that is curable by ultraviolet rays, electron beams or other active energy rays. <P>SOLUTION: The composition for a coating with good touch comprises a compound having a specific structure. The composition for a coating with good touch comprises the compound having a specific structure and a reactive diluent and/or a photopolymerization initiator. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to tactile paint compositions.

  Although paints are widely used in various fields, tactile paints that can provide a coating with a “moist feeling” may be used for automobile interior parts and plastic parts of household electrical appliances to provide a high-class feel. .

  As a touch-sensitive paint, for example, a paint containing polyurethane resin, isocyanate, urethane beads and polyglycerin fatty acid ester has been proposed (see Patent Document 1). Has come to be demanded.

  In order to respond to such a demand, an ultraviolet curable leather-like paint composition using an ultraviolet curable monomer and a silicon compound has been proposed (see Patent Document 2), but further improvement has been demanded.

  By the way, although this applicant has proposed the polyurethane acrylate as a clear coating agent (refer patent document 3), no examination was carried out about the tactile property of the said clear coating agent.

JP 2005-344049 A JP 2006-257366 A JP-A-2-274713

  The present invention is characterized by providing a tactile sensation paint that can be cured with active energy rays such as ultraviolet rays and electron beams having good tactile sensation.

  As a result of intensive studies to solve the above-mentioned problems, the present inventor has found that tactile sensation can be improved by containing a specific number or more of specific structures in polyurethane acrylate. That is, the present invention relates to the general formula (1):

(Wherein X ¹ is an alkylene group having 3 to 6 carbon atoms which may have a branched structure, and R ¹ is a general formula (2): CH ₂ ═CR ³ —COO—X ² —O— (wherein , R ³ represents a hydrogen atom or a methyl group, X ² represents an alkylene group having 1 to 4 carbon atoms, and R ² represents a general formula (3) CH ₂ ═CR ⁴ —COO—X ^{3 -O- (CO-X 4 -O} ) m - ( wherein, ^{R 4} is a hydrogen atom or a methyl group, ^{X 3} is an alkylene group having 1 to 4 carbon atoms, ^{X 4} is also have a branched structure A functional group represented by a good alkylene group having 3 to 6 carbon atoms, m represents an integer of 0 to 8, and n represents an integer of 2 to 8. In addition, each of X ¹ , X ² and R ¹ , R ³ and n may be the same or different.) And a tactile paint composition comprising the compound represented by:

  ADVANTAGE OF THE INVENTION According to this invention, the tactile-coating composition excellent in tactile property can be provided. Moreover, scratch resistance can also be improved by making the number of repeating units of the polyester structure in polyurethane acrylate into a specific range.

  The tactile paint composition of the present invention has the general formula (1):

(Wherein X ¹ is an alkylene group having 3 to 6 carbon atoms which may have a branched structure, and R ¹ is a general formula (2): CH ₂ ═CR ³ —COO—X ² —O— (wherein , R ³ represents a hydrogen atom or a methyl group, X ² represents an alkylene group having 1 to 4 carbon atoms, and R ² represents a general formula (3): CH ₂ = CR ⁴ —COO— X ³ —O— (CO—X ⁴ —O) _m — (wherein R ⁴ is a hydrogen atom or a methyl group, X ³ is an alkylene group having 1 to 4 carbon atoms, and X ⁴ has a branched structure. Or an alkylene group having 3 to 6 carbon atoms, m represents an integer of 0 to 8.), and n represents an integer of 2 to 8. In addition, each X ¹ , X ² , R ¹ , R ^3, and n may be the same or different from each other). In general formula (1), it is preferable to set the value of n to 4 to 6 because scratch resistance can be improved.

  The compound represented by the general formula (1) is represented by the general formula (4):

1,3,5-tris (isocyanatohexyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) trione represented by general formula (5): CH ₂ ═CR ³ -COO-X ² -O- (CO-X ¹ -O) _n H (wherein R ³ is a hydrogen atom or a methyl group, X ¹ is a C 3-6 which may have a branched structure) An alkylene group, X ² represents an alkylene group having 1 to 4 carbon atoms, and n represents an integer of 2 to 8.) and a general formula (6): CH ₂ = CR ⁴ —COO—X ³ —O— (CO—X ⁴ —O) _m —H (wherein R ⁴ is a hydrogen atom or a methyl group, X ³ is an alkylene group having 1 to 4 carbon atoms, and X ⁴ has a branched structure) A good alkylene group having 3 to 6 carbon atoms, m represents an integer of 0 to 8.) It can be obtained by. The compound represented by the general formula (4) is, for example, a compound obtained by trimerizing hexamethylene diisocyanate, but a commercially available product may be used as it is. Examples of the compound represented by the general formula (5) include hydroxy acrylates such as 2-hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate. It can be obtained by reacting a lactone such as ε-caprolactone, δ-valerolactone, or γ-valerolactone. For example, when R ³ is a hydrogen atom, X ² is an ethylene group, and X ¹ is a pentylene group, 2-hydroxyethyl acrylate and ε-caprolactone may be reacted by a known method. Note that n can be controlled by adjusting the caprolactone used. A compound represented by the general formula (6) can also be prepared by a similar method. As the compound represented by the general formula (5), R ³ is a hydrogen atom, X ¹ is alkylene group of 5 carbon atoms, X ² is an alkylene group having 2 carbon atoms, when n is 4 to 6 Preferably, as the compound represented by the general formula (6), R ⁴ is a hydrogen atom, X ³ is an alkylene group having 2 to ³ carbon atoms, X ⁴ is an alkylene group having 5 carbon atoms, and m is 0 to 6. The case is preferred.

In addition, the usage-amount of the compound represented by the compound represented by the compound represented by General formula (4), the compound represented by General formula (5), and General formula (6) is normally represented by General formula (4). About 1 to 3 mol of the compound represented by the general formula (5) and about 0 to 1.5 mol of the compound represented by the general formula (6) with respect to 1 mol of the compound, 4 to 3 mol of the compound represented by the general formula (5) and 0 to 1 mol of the compound represented by the general formula (6) with respect to 1 mol of the compound represented by 4). When the general formula (5) and the general formula (6) are the same structural formula, the compound represented by the general formula (5) and the general formula (5) with respect to 1 mol of the compound represented by the general formula (4) The total amount of the compound represented by 6) may be 3 mol.

In order to react these components, a known method may be employed. Specifically, for example, the compound represented by the general formula (4), the compound represented by the general formula (5), and the compound represented by the general formula (6) may be charged and reacted in a lump. In addition, you may use catalysts, such as stannous octylate and dibutyltin dilaurate, as needed. When the catalyst is used, the amount used is 0 with respect to a total of 100 parts by weight of the compound represented by the general formula (4), the compound represented by the general formula (5) and the compound represented by the general formula (6). About 0.01 to 0.05 weight. Usually, the reaction may be performed at about 70 to 80 ° C. for about 2 to 3 hours. In addition, you may add a well-known polymerization inhibitor as needed.

The tactile paint composition of the present invention contains the compound represented by the general formula (1). The content of the compound represented by the general formula (1) is not particularly limited, but the compound represented by the general formula (1) is usually 50 to 100 parts by weight, preferably 80, in 100 parts by weight of the tactile paint composition. ˜100 parts by weight. In addition, the touch-sensitive coating composition of the present invention may further contain a reactive diluent, a photopolymerization initiator, an additive, a pigment, and the like as necessary.

The reactive diluent is not particularly limited as long as it is a reactive diluent that can be used for an active energy ray-curable coating material, and a known one can be used. The reactive diluent may be monofunctional or polyfunctional, and may be used singly or in appropriate combination. Specific examples include styrene monomers and acrylic monomers. Specifically, examples of the styrenic monomer include styrene, α-methylstyrene, vinyl toluene, and the like. Examples of acrylic monomers include tripropylene glycol diacrylate, tetraethylene glycol diacrylate, trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, bisphenol A tetraethylene glycol diacrylate, hexamethylene glycol diacrylate, and 1,9-nonanediol. Examples include diacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, N-vinylpyrrolidone, N-vinylformamide, 4-hydroxybutyl vinyl ether, diethylene glycol divinyl ether, and the like. Further, urethane acrylates obtained by reacting polyisocyanates with hydroxyl acrylate may be used. Etc. Although the usage-amount at the time of using a reactive diluent is not specifically limited, Usually, it is preferable to set it as about 5-30 weight part with respect to 100 weight part of compounds represented by General formula (1). It does not specifically limit as a photoinitiator, A well-known thing can be used. The photopolymerization initiator is usually used when cured with ultraviolet rays, and may not be used when cured with an electron beam.

It does not specifically limit as a photoinitiator, Various well-known things can be used as it is. Specific examples include benzophenone, o-benzoylbenzoic acid methyl ester, p-dimethylaminobenzoic acid ester, p-dimethylacetophenone, thioxanthone, alkylthioxanthone, and amines. Commercially available products such as Darocur 1173, Irgacure 651, Irgacure 184, Irgacure 907, Irgacure 2959 (manufactured by Ciba Specialty Chemicals) may be used as they are. Although the usage-amount at the time of using a photoinitiator is not specifically limited, Usually, it is preferable to set it as about 1-5 weight part with respect to 100 weight part of compounds represented by General formula (1). As an additive, the additive normally used for a coating material can be used.

  EXAMPLES Hereinafter, although a manufacture example, an Example, and a comparative example are given and this invention is demonstrated concretely, this invention is not limited to these each example.

Production Example 1
In a 1 liter four-necked flask equipped with a stirrer, thermometer and condenser, 1,3,5-tris (isocyanatohexyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) Trione (trade name Coronate HX, Nippon Polyurethane Industry Co., Ltd., isocyanate group content 21%) 150 g (0.25 mol), ε-caprolactone-β-hydroxyethyl acrylate adduct (caprolactone of hydroxyethyl acrylate) 429 g (0.75 mol) of 4-mol adduct, trade name Plaxel FA-4, manufactured by Daicel Chemical Industries, Ltd., and 0.58 g (1000 ppm) of 4-methoxyphenol were gradually heated while stirring. While paying attention to the exothermic state due to the reaction, the temperature was raised to 75 ° C. over 1.5 hours, kept at 75-80 ° C. for 1 hour, and then 0.12 g (200 ppm) of stannous octoate was added and further 1 hour Keep warm. After confirming the disappearance of the remaining isocyanate group by IR, the mixture was cooled to obtain 579 g of a pale yellow viscous liquid. This was designated as Resin A.

Production Example 2
A reactor similar to Production Example 1 was charged with 150 g (0.25 mol) of Coronate HX, 286 g (0.50 mol) of Plaxel FA-4, and 29 g (0.25 mol) of 2-hydroxyethyl acrylate. Reaction was performed in the same manner as in 1 to obtain 465 g of a pale yellow viscous liquid. This was designated as Resin B.

Production Example 3
In the same reactor as in Production Example 1, 150 g (0.25 mol) of coronate HX, ε-caprolactone-β-hydroxyethyl acrylate adduct (hydroxypropyl acrylate 6 mol adduct, trade name Plaxel FA-6, Daicel Chemical) Kogyo Co., Ltd.) was charged in the same manner as in Production Example 1 to obtain 750 g of a pale yellow viscous liquid. This was designated as Resin C.

Comparative production example 1
A reactor similar to Production Example 1 was charged with 150 g (0.25 mol) of Coronate HX, 143 g (0.25 mol) of Plaxel FA-4, and 58 g (0.5 mol) of 2-hydroxyethyl acrylate. The reaction was carried out in the same manner as in 1 to obtain 351 g of a pale yellow viscous liquid. This was designated as Resin D.

Comparative production example 2
A reactor similar to Production Example 1 was charged with 150 g (0.25 mol) of Coronate HX and 87 g (0.75 mol) of 2-hydroxyethyl acrylate, and reacted in the same manner as in Production Example 1 to obtain 237 g of a pale yellow viscous liquid. Got. This was designated as Resin E.

Comparative production example 3
In the same reactor as in Production Example 1, 111 g (0.5 mol) of isophorone diisocyanate and 572 g (1 mol) of Plaxel FA-4 were charged and reacted in the same manner as in Production Example 1 to obtain 683 g of a pale yellow viscous liquid. Got. This was designated as Resin F.

Comparative production example 4
In the same reactor as in Production Example 1, 271 g (1.22 mol) of isophorone diisocyanate and 265 g (0.53 mol) of polyester diol (cocondensate of adipic acid and 1,4-butanediol, average molecular weight 500) ), 160 g (1.38 mol) of 2-hydroxyethyl acrylate, and the reaction was conducted in the same manner as in Production Example 1 to obtain 696 g of a pale yellow viscous liquid. This was designated as Resin G.

Example 1
A composition comprising 50 parts by weight of the resin A obtained in Production Example 1, 50 parts by weight of methyl ethyl ketone as a solvent, and 2.5 parts by weight of a photopolymerization initiator (trade name Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) After mixing, a tactile paint composition was prepared and subjected to the following test.

Examples 2 and 3 and Comparative Examples 1 to 4
A tactile paint composition was prepared by mixing the same composition as in Example 1 except that the resin A was changed to resins B to G, and subjected to the following tests.

Example 4
50 parts by weight of the resin A obtained in Production Example 1, 20 parts by weight of trimethylolpropane triacrylate (trade name Biscote # 295, manufactured by Osaka Organic Chemical Co., Ltd.) as a reactive diluent, 30 parts by weight of methyl ethyl ketone as a solvent, and light A composition comprising 3.5 parts by weight of a polymerization initiator was mixed to prepare a sample, which was subjected to the following test.

Examples 5 and 6 and Comparative Examples 5 to 8
A sample was prepared by mixing the same composition as in Example 6 except that the resin A was changed to resins B to G, and subjected to the following tests.

<Various performance test methods>
1. Tactile test The obtained sample was applied on a polycarbonate plate with an applicator by a dry film thickness of 20 μm and dried at 80 ° C. for 2 minutes. This was irradiated with a high-pressure mercury lamp and cured (120 W / cm × 10 cm (height) × 1 lamp × 10 m / min × 3 passes), and this was used as a cured coating film. The tactile sensation was determined by touching the surface of the cured coating film with a finger and determining the moist feeling by the way the finger was caught. The results are shown in Table 1. Tactile sensation ○ ······ Moist tactile sensation with fingers caught.
Δ ····· Moist feeling with a little finger catching.
× ······························································································· There is no moist touch.

2. Scratchability test The same cured coating film surface as in the tactile sensation test was strongly rubbed with a toe, and the scratchability of the surface was visually determined. The results are shown in Table 1.
○ ·····························································································································

Claims (4)

General formula (1):

(Wherein X ¹ is an alkylene group having 3 to 6 carbon atoms which may have a branched structure, and R ¹ is a general formula (2): CH ₂ ═CR ³ —COO—X ² —O— (wherein , R ³ represents a hydrogen atom or a methyl group, X ² represents an alkylene group having 1 to 4 carbon atoms, and R ² represents a general formula (3) CH ₂ ═CR ⁴ —COO—X ^{3 -O- (CO-X 4 -O} ) m - ( wherein, ^{R 4} is a hydrogen atom or a methyl group, ^{X 3} is an alkylene group having 1 to 4 carbon atoms, ^{X 4} is also have a branched structure A functional group represented by a good alkylene group having 3 to 6 carbon atoms, m represents an integer of 0 to 8, and n represents an integer of 2 to 8. In addition, each of X ¹ , X ² and R ¹ , R ³ and n may be the same or different.) And a tactile paint composition comprising the compound represented by: The tactile paint composition according to claim 1, wherein n is 4 to 6 in the general formula (1). Furthermore, the tactile-coating composition of Claim 1 or 2 containing a reactive diluent. Furthermore, the tactile-coating composition in any one of Claims 1-3 containing a photoinitiator.