JPH07292283A - Thermosetting resin composition for in-mold coating - Google Patents

Abstract

PURPOSE:To obtain the subject composition making it possible to obtain a molding with a coating layer from which deposited stains can be readily removed and which is excellent in recovery from staining. CONSTITUTION:This thermosetting resin composition for a coating material for in-mold coating is obtained by mixing 100 pts.wt. thermosetting resin component containing a thermosetting resin and a copolymerizable monomer with 0.5-5.0 pts.wt. silane monomer represented by the formula (wherein R1, R2 and R3 are each independently phenyl or a 1-10C alkyl group; (m) is 0 to 10; and Y1 is an atomic group having an ethylenic double bond).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermosetting coating used in an in-mold coating molding method for coating a thermosetting coating material on the surface of a thermosetting molding material in a mold and curing the coating to form a coating layer. The present invention relates to a material, particularly to a thermosetting resin composition for in-mold coating molding which is excellent in stain recovery.

[0002]

2. Description of the Related Art Recently, molded articles made of thermosetting material have
It is widely used in industrial parts as a substitute for metal parts. Above all, sheets reinforced with glass fiber
Molding compound (hereinafter SMC) or
Bulk Molding Compound (hereinafter BMC)
Is commonly used.

However, a molded product obtained by molding SMC and BMC by heating and pressing in a mold tends to have surface defects such as pinholes, microcracks, sink marks or undulations on the surface. . When such surface defects are present, it is difficult to form a sufficient coating film even if the molded product is coated by a usual method.

Therefore, a so-called in-mold coating molding method has been proposed as a method for concealing the above-mentioned surface defects. For example, Japanese Examined Patent Publication No. 4-33252 discloses a method of forming a coating layer on a molding material by injecting the coating material at a pouring pressure higher than the molding pressure and curing it during compression molding.

Further, as a thermosetting resin composition for in-mold coating molding used as a coating material in these molding methods, for example, Japanese Patent Publication No. 1-35856 discloses urethane acrylate as a main component and α, β. -In-mold coating molding compositions using an ethylenically unsaturated copolymer and a filler are disclosed.

[0006]

However, the coating layer coated by the conventional in-mold coating molding method has a problem that the stain recovery property is poor.

An object of the present invention is to provide a thermosetting resin composition for in-mold coating molding, which can easily remove adhered stains and can obtain a coated molded article excellent in stain recovery. .

[0008]

The thermosetting resin composition for in-mold coating according to claim 1 comprises a silane monomer represented by the following general formula (1), a thermosetting resin and a copolymer. To 100 parts by weight of thermosetting resin containing a polymerizable monomer,
It is characterized by containing 0.5 to 5.0 parts by weight.

[0009]

[Chemical 4]

In the above formula (1), R _{1 to} R ₃ are independently of each other a phenyl group or an alkyl group having 1 to 10 carbon atoms, m is 0 or an integer of 1 to 10, and Y ₁ is an ethylenic double bond. Represents an atomic group having.

The thermosetting resin composition for in-mold coating molding according to claim 2 is a copolymer of a thermosetting resin and a reactive siloxane oligomer represented by the following general formula (2) or (3). It is characterized in that 0.1 to 2.5 parts by weight is contained with respect to 100 parts by weight of the thermosetting resin containing a polymerizable monomer.

[0012]

[Chemical 5]

In the above formula (2), R _{4 to} R ₉ are independently of each other an alkyl group having 1 to 6 carbon atoms or a phenyl group, Y ₂ is an atomic group having an ethylenic double bond, and Y ₃ is an ethylenic group. Atomic group having double bond or hydrogen, n is 0
Or an integer of 1 to 5, k is 0 or an integer of 1 to 10, l
Represents 0 or an integer of 1 to 5.

[0014]

[Chemical 6]

In the above formula (3), R ₁₀ and R ₁₇ are independent of each other and R _{11 to} R ₁₆ are methylene chains having 2 to 5 carbon atoms and having a portion bonded by one phenylene group.
Are independently of each other an alkyl group having 1 to 6 carbon atoms, Y ₄ ,
Y ₅ represents an atomic group having ethylenic double bonds independent of each other, and p represents 0 or an integer of 1 to 5.

The present invention will be described in detail below. Silane monomer The silane monomer according to claim 1 is 0.5 to 5.0 parts by weight based on 100 parts by weight of the total amount of the thermosetting resin, the copolymerizable monomer, and the low-shrinking agent resin added as necessary. It is added in the range, preferably in the range of 1.0 to 3.0 parts by weight. If it is less than 0.5 parts by weight, the effect of improving the stain recovery is not obtained, and if it is more than 5.0 parts by weight, the adhesion between the coating layer and the molded article substrate is lowered, or the strength of the coating layer is lowered. Such disadvantages occur.

In the above formula (1), R _{1 to} R ₃ are each independently an alkyl group having 1 to 10 carbon atoms or a phenyl group, preferably a linear alkyl group having 1 to 5 carbon atoms. is there. A silane monomer having an alkyl group having more than 10 carbon atoms has a drawback that it is difficult to synthesize.

M is 0 or an integer in the range of 0 to 10, preferably in the range of 0 to 5, and more preferably 0 to 3. If m exceeds 10, there is a drawback that the silane monomers agglomerate with each other to lower the dispersibility and the reactivity of the silane monomer.

Y ₁ is a characteristic group having an ethylenic double bond. Specific examples thereof include a methacryloyl group, an acryloyl group, an alkenyl group and a styryl group.

Siloxane Oligomer The siloxane oligomer represented by the formula (2) or (3) according to claim 2 is a thermosetting resin, a copolymerizable monomer,
And a total amount of the low-shrinking agent resin added as necessary 10
It is added in an amount of 0.1 to 2.5 parts by weight, preferably 0.7 to 1.5 parts by weight, based on 0 parts by weight. If it is less than 0.1 part by weight, the effect of improving the pollution recovery is not obtained, and it is 2.5
If the amount is more than the amount by weight, there are disadvantages such as a decrease in adhesion between the coating layer and the molded article base material and a reduction in strength of the coating layer.

In the formula (2), R _{4 to} R ₉ are independently of each other an alkyl group having 1 to 6 carbon atoms or a phenyl group, preferably a linear alkyl group having 1 to 3 carbon atoms. A siloxane oligomer having an alkyl group or a phenyl group having more than 6 carbon atoms has a drawback that it is difficult to synthesize.

Y ₂ and Y ₃ are atomic groups having an ethylenic double bond. Specific examples thereof include a methacryloyl group, an acryloyl group, an alkenyl group and a styryl group.
Further, Y ₃ may be hydrogen. In this case, the terminal of the methylene chain bonded to the silane becomes a methyl group.

K is 0 or an integer in the range of 1 to 10, preferably 0 or an integer in the range of 1 to 5, and more preferably 0 or an integer in the range of 1 to 2. k is 1
If it exceeds 0, there is a drawback that the molecular weight of the siloxane oligomer increases and the dispersibility decreases.

N is 0 or an integer of 1 to 5,
It is preferably 0 or 1 to 3. When n exceeds 5, the molecular weight of the siloxane oligomer increases and the dispersibility decreases. l is 0 or an integer of 1 to 5, preferably 0 or 1 to 3, and when l exceeds 5, the molecular weight of the siloxane oligomer increases and the dispersibility decreases.

In the above general formula (3), R ₁₀ ,
R ₁₇ is independent of each other, and has a methylene chain having 2 to 5 carbon atoms and having a moiety bonded by one phenylene group,
Preferred is a methylene chain having 3 carbon atoms. When the number of carbon atoms in the methylene chain exceeds 5, the dispersibility of the siloxane oligomer tends to deteriorate.

R _{11 to} R ₁₆ are each independently an alkyl group having 1 to 6 carbon atoms, preferably 1 to 6 carbon atoms.
3 is an alkyl group. When the number of carbon atoms in the alkyl group exceeds 6, the molecular weight becomes large and the dispersibility of the siloxane oligomer decreases.

Each of Y ₄ and Y ₅ is an atomic group having an ethylenic double bond independent of each other, and specific examples thereof include a methacryloyl group, an acryloyl group, an alkyl group, or a styryl group. .

Further, p is 0 or an integer of 1 to 5, preferably 0 or 1 or 2, and when p exceeds 5, the molecular weight of the siloxane oligomer increases and the dispersibility decreases.

Examples of Silane Monomers Examples of the silane monomer according to claim 1 are vinyltrimethylsilane (used in Example 1 described later), vinyldiethylmethylsilane (Example 5) and vinyltriphenylsilane (Example 6). ), Phenyldimethylsilylmethylmethacrylate (Example 7), allyltrimethylsilane (Example 2), 2-bropenyltrimethylsilane (Example 4), trimethylsilylmethylacrylate (Example 3), trimethylsilylmethylmethacrylate, propenyldimethyl. Silylmethylmethacrylate, 3-methacryloxypropyltrimethylsilane, phenyldimethylsilylmethylacrylate, propenyldimethylsilylmethylacrylate, 3-acryloxypropyltrimethylsilane, allyltriethylsilane, trif Alkenyl vinyl silane, 4-butenyl-trimethylsilane, hexa -5
-Enyltrimethylsilane, octa-7-enyltrimethylsilane, phenylallyldimethylsilane, phenyldimethylvinylsilane, vinyl-i-propyldimethylsilane, vinyl-t-butyldimethylsilane, vinylpentyldimethylsilane, allylpentyldimethylsilane, styryltrimethylsilane Examples thereof include silane, styrylethyltrimethylsilane, styrylethyltriethylsilane, and styrylethylphenyldimethylsilane.

Examples of siloxane oligomers The siloxane oligomers of claim 2 are:
3-divinyltetramethyldisiloxane (used in Example 9 below), 1,3-bis (3-methacryloxypropyl) tetramethyldisiloxane (Example 8), 1,3-
Bis {(p-acryloxymethyl) phenethyl} tetramethyldisiloxane (Example 11), 1,3-divinyldodecamethylhexasiloxane (Example 12), 1,3
-Divinylecosamethyldecasiloxane (Example 1
3), 3-methacryloxypropyl pentamethyldisiloxane (Example 14), divinyl-1,3-diphenyl-1,3-dimethyldisiloxane (Example 10), 1,
3-divinyltetramethyldisiloxane, 1,3-bis {(p-methacryloxymethyl) phenethyl} tetramethyldisiloxane, 1,3-bis (3-acryloxypropyl) tetramethyldisiloxane, 1,3-divinyl Hexamethyltrisiloxane, 3-methacryloxypropyl-1,3-diphenyl-1,3-dimethyldisiloxane, 3-acryloxypropylpentamethyldisiloxane, vinylheptamethyltrisiloxane and the like can be mentioned.

Thermosetting Resin Examples of the resin used as the thermosetting resin in the thermosetting resin composition for in-mold coating molding used in the present invention include unsaturated polyester resin, urethane acrylate resin, epoxy acrylate resin and the like. Used.

Here, as the unsaturated polyester resin, an organic polyol, an aliphatic unsaturated polycarboxylic acid, and, if necessary, an aliphatic saturated polycarboxylic acid and / or an aromatic can be used by a known and commonly used method. The thing manufactured from polycarboxylic acid etc. is used.

As the urethane acrylate resin,
A conventionally known and conventional one is used. For example, it is produced by reacting an organic polyol such as an alkylene diol, an alkylene diol ester, an alkylene diol ether, a polyether polyol or a polyester polyol with an organic polyisocyanate and further reacting with a hydroxyalkyl (meth) acrylate.

On the other hand, as the epoxy acrylate resin, on the other hand, a reaction product of an epoxy resin and a monocarboxylic acid having a reactive double bond such as (meth) acrylic acid is usually polymerized with styrene, diacrylic phthalate or the like. What was melt | dissolved in the unsaturated monomer is used.

Here, examples of the above-mentioned organic polyol include diols, triols, tetraols and mixtures thereof, and they are mainly divided into aliphatic polyols and aromatic polyols, and of these, typical ones are aliphatic polyols. Includes ethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, triethylene glycol, neopentyl glycol, dibromoneopentyl glycol, hexamethylene glycol, trimethylene glycol, trimethylolpropane, glycerin, pentaerythritol diallyl ether, There are hydrogenated bisphenol A, and typical aromatic polyols include bisphenol A.
Alternatively, polyoxyalkylene bisphenol A or polyoxyalkylene bisphenol S obtained by adding an aliphatic oxirane compound such as ethylene oxide, propylene oxide, or butylene oxide to bisphenol S in an average of 1 to 20 per molecule There is.

As the epoxy resin used for the above-mentioned epoxy acrylate resin, a bisphenol A type epoxy resin produced from epichlorohydrin and bisphenol A and a brominated bisphenol A produced from epichlorohydrin and brominated bisphenol A by a known method. -Type epoxy resin, phenol novolac or ortho-cresol novolac is converted into glycidyl ether to produce novolac-type epoxy resin, glycidylamine-type epoxy resin obtained by reacting various amines with epichlorohydrin (tetraglycidyl metaxylenediamine, tetraglycidyl 1 , 3-bisaminomethylcyclohexane, tetraglycidylaminodiphenylmethane, triglycidyl-p-aminophenol, triglycidyl -m- aminophenol, diglycidyl aniline, diglycidyl ortho-toluidine, etc.) and the like.

Examples of the polyol used for the urethane acrylate resin include alkylene diols such as ethylene glycol, propylene glycol, diethylene glycol, diisopropylene glycol, polyethylene glycol, polypropylene glycol, and hydroxyalkyl ether of butanediol. As the ether polyol, polyoxymethylene, polyethylene oxide, polypropylene oxide and the like are used, and as the polyester polyol, the above-mentioned organic polyol and polyester polyol having hydroxyl groups at both ends produced by polycarboxylic acid are used.

As the polyisocyanate used for the urethane acrylate resin, tolylene diisocyanate, isophorone diisocyanate, polymethylene polyphenyl diisocyanate, etc. are used.

The hydroxyalkyl (meth) acrylate used in the urethane acrylate resin is usually hydroxyethyl (meth) acrylate,
Hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate and the like are used, and the hydroxyl group is usually bonded to the carbon at the beta position of the alkyl group. Alkyl groups can usually contain up to 8 carbon atoms.

Copolymerizable Monomer Further, the thermosetting resin composition for in-mold coating molding used in the present invention may contain styrene, alphamethylstyrene, divinylbenzene, vinyltoluene, diallylphthalate, various kinds, etc., if necessary. Copolymerizable monomers such as acrylate monomers and various methacrylate monomers can be added. When adding these copolymerizable monomers, the amount of the resin component (thermosetting resin and copolymerizable monomer)
Of these, 1 to 70% by weight is preferable, and 3 to 50% by weight is more preferable. If the amount added is too small, the viscosity of the coating material increases, so that there is a drawback that it is difficult to obtain sufficient fluidity when pouring the coating material. On the contrary, if the amount added is too large, the adhesiveness will decrease.

Low shrinkage agent In addition, in the thermosetting resin composition for in-mold coating molding used in the present invention, as the low shrinkage agent, polyvinyl acetate, polymethyl (meth) acrylate, polyethylene, ethylene vinyl acetate copolymer is used. , Thermoplastic resins such as vinyl acetate-styrene copolymers, polybutadiene, saturated polyesters, saturated polyethers and the like can be added. When adding these thermoplastic resins, as the amount,
0.1 to 30 wt% of the total resin content (in the present invention, the total resin content refers to the total amount of the thermosetting resin, the copolymerizable monomer, and the low-shrinking agent added as necessary) Is more preferable, and more preferably 0.3 to 15% by weight. If the amount added is too large, the viscosity of the coating material increases, so that there is a drawback that it is difficult to obtain sufficient fluidity when pouring the coating material. On the other hand, if the amount added is too small, it is difficult to obtain a sufficient shrinkage improving effect.

Other Ingredients Furthermore, the above thermosetting resin composition for in-mold coating molding,
Ketone peroxides, diacyl peroxides,
Known initiators such as hydroperoxides, dialkyl peroxides, alkyl peresters, percarbonates and peroxyketals; known curing accelerators such as dimethylaniline and cobalt naphthenate; polymerization inhibition of parabenzoquinone etc. Agents; metal soaps such as zinc stearate; release agents such as aliphatic phosphates and lecithin; stabilizers such as phosphite compounds and phenol compounds, etc., can be added in appropriate amounts according to the use and purpose. .

Molding Material for Molded Article Base Material Used in Combination Also, the thermosetting resin composition used as the molding material for the molded article base material in the present invention is the same as the thermosetting resin composition coated in the mold. The materials are appropriately mixed and used. That is, an unsaturated polyester resin, a vinyl ester resin, a urethane acrylate resin or the like is used as the thermosetting resin, and if necessary, various copolymerizable monomers, a low shrinkage agent,
Various fillers, colorants, initiators, reinforcing materials, additives and the like can be added.

As a particularly general-purpose example of such a molding material, for example, an unsaturated polyester resin is dissolved in styrene, a low-shrinking agent made of a thermoplastic resin is added, and an organic peroxide as an initiator is used. It has been conventionally known that SMC or BMC is added by adding various fillers and reinforcing agents such as glass fiber.

More specifically, for example, 60 to 100 parts by weight of a styrene solution of an unsaturated polyester resin (styrene concentration: 40 to 70% by weight) is added to a thermoplastic resin such as polymethylmethacrylate, polystyrene or polyvinyl acetate. Styrene solution (styrene concentration 30-80% by weight) 0
~ 40 parts by weight to make 100 parts by weight, and a filler 10 such as calcium carbonate, aluminum hydroxide, glass powder, etc.
0 to 300 parts by weight, thickener such as magnesium oxide 0.1
To 3 parts by weight, 0.1 to 5 parts by weight of an organic peroxide such as t-butylperoxobenzoate, and 0.5 to 5 parts by weight of a release agent such as zinc stearate, and kneaded to reinforce glass fiber or the like. 10 to 200 parts by weight of material is impregnated with SMC or BM
The form of C is preferably used.

Molding The thermosetting resin composition for in-mold coating molding of the present invention obtained as described above is used together with SMC or BMC in a conventionally known in-mold coating molding method.

For example, SMC is put into a molding die heated to 130 to 160 ° C., and pressure is applied at a pressure of 40 to 120 kg / cm ² for 30 to 300 seconds, and then the die is slightly opened to cover the coating material. Injection, then 5-120 kg / c
There is a method in which the coating material is spread over the entire surface of the molded SMC by reheating and pressurizing at m ² of 130 to 160 ° C. for 30 to 300 seconds and then cured to form a coating layer.

Further, as disclosed in Japanese Examined Patent Publication No. 4-33252, SMC at 130 to 160 ° C., 40 to 12
After pressure molding several tens of seconds to several minutes at 0 kg / cm ^2, was injected coating material at high pressure 100 to 300 / cm ² using a high pressure injection machine in a state where the pressure was reduced to 10 to 30 kg / cm ² There is also a method of increasing the pressure again to 30 to 100 kg / cm ² to spread-harden the coating material.

[0049]

In the invention described in claim 1, as the coating material,
A thermosetting resin composition obtained by adding a specific silane monomer to the thermosetting resin is used. Therefore, the coating layer formed of the silane monomer having a low surface free energy has a high hydrophobicity, which can improve the stain recovery property of the coating layer.

According to the second aspect of the invention, a thermosetting resin composition obtained by adding a specific siloxane oligomer to a thermosetting resin is used as the coating material. Therefore, the coating layer formed of the siloxane oligomer having a low surface free energy has a high hydrophobicity, which can improve the stain recovery property of the coating layer.

[0051]

EXAMPLES Non-limiting examples of the present invention will be described below. In the following, parts mean parts by weight unless otherwise specified.

Preparation of SMC 1. 70 parts of unsaturated polyester resin liquid (about 60 wt% of isophthalic acid-based unsaturated polyester resin dissolved in about 40 wt% of styrene monomer) Polystyrene low-shrinking agent resin (about 30% by weight of polystyrene resin dissolved in about 70% by weight of styrene monomer) 30 parts 3. 120 parts of calcium carbonate powder (NS-100: Nitto Koka Co., Ltd.) 4. Curing agent (Kayabutyl B: Kayaku Akzo Co., tertiary butyl peroxobenzoate content 98% by weight)
Part 1. Thickener (magnesium oxide powder, Kyowamag 15)
0: made by Kyowa Chemical Industry Co., Ltd.) 1. Internal mold release agent (zinc stearate: Sakai Chemical Industry Co., Ltd.)
6. After mixing 3 parts or more of the materials and thoroughly stirring, use an SMC impregnation device. 60 parts of glass fiber (Roving made by Asahi Fiber Glass Co., Ltd .: ER4630LBD166W cut into a length of 25 mm) was impregnated with 60 parts to obtain SMC. 8. The obtained SMC was aged at 40 ° C. for 24 hours.

Preparation of coating material 1. Thermosetting resin liquid: 1) Epoxy acrylate resin liquid (bisphenol-based epoxy resin converted to methacrylic acid ester, number average molecular weight about 2000, styrene concentration in resin about 40% by weight: Showa High Polymer Co., Ltd.) 2) Urethane acrylate resin (manufactured by Negami Kogyo Co., Ltd .:
A urethane acrylate resin liquid prepared by adjusting UN5200) so that the styrene concentration in the resin is about 30% by weight.

2. As silane monomer 1): Vinyltrimethylsilane (manufactured by Chisso Corporation) 2): Allyltrimethylsilane (manufactured by Chisso Corporation) 3): Trimethylsilylmethylmethacrylate (manufactured by Chisso Corporation) 4): 2-propenyltrimethylsilane (Chisso Corporation) 5): Vinyltriethylsilane (manufactured by Chisso Corporation) 6): Vinyltriphenylsilane (manufactured by Chisso Corporation) 7) Phenyldimethylmethylsilyl methacrylate (manufactured by Chisso Corporation)

3. As a siloxane oligomer 8) 1,3-bis (3-methacryloxypropyl) tetramethyldisiloxane (manufactured by Chisso Corporation) 9) 1,3-divinyltetramethyldisiloxane (manufactured by Chisso Corporation) 10) Divinyl-1, 3-diphenyl-1,3-dimethyldisiloxane (manufactured by Chisso Corporation) 11) 1,3-bis {(acryloxymethyl) phenethyl} tetramethyldisiloxane (manufactured by Chisso Corporation) 12) 1,3-divinyldodeca Methyl hexasiloxane (manufactured by Toshiba Silicone Co., Ltd.) 13) 1,3-divinylicosamethyldecasiloxane (manufactured by Toshiba Silicone Co., Ltd.) 14) 3-methacryloxypropylpentamethyldisiloxane (manufactured by Chisso Corporation) Blended in the amount shown in 2 with respect to 100 parts of the thermosetting resin liquid

4. Extender pigment: calcium carbonate (NS-1
00: Nitto Koka Kogyo Co., Ltd., average particle size 2 μm) 50
Part 5. Curing agent: tertiary peroxobenzoate (Kayabutyl B: manufactured by Kayaku Akzo) 1 part 6. A white coating material was obtained by adding 40 parts of a white pigment (titanium oxide, SR-1, manufactured by Sakai Chemical Industry Co., Ltd., average particle size: about 0.24 μm) and thoroughly stirring and kneading.

Molding Using a 300 ton press, a 300 mm × 300 mm square flat plate mold is 135 ° C. for the upper mold and 115 ° C. for the lower mold.
After heating to 400 g, the SMC is charged with 400 g (thickness 4
mm) and press-molded at a press pressure of 100 kg / cm ² for 400 seconds. After that, the mold was slightly opened, and 12 ml of the coating material was injected. After injecting the coating material, the mold was closed again, and heated and pressed at a pressing pressure of 70 kg / cm ² for 300 seconds to obtain a molded article coated with the coating material.

Evaluation Three test pieces each having a size of 50 × 50 mm were cut out from the center of the obtained molded product, and each contaminated molded product was evaluated by the following method. (1) Rubbing the surface of the test piece 20 times with a cloth soaked with 5% by weight of soap and water, washing with water, and then drying with an air dryer at a temperature of 50 ± 3 ° C. for 30 minutes, and photoelectric color Total (J
The diffuse reflectance of the central portion of the test piece (referred to as the stimulus value Y defined in JIS Z8772) is measured by using a device conforming to IS Z8722) and designated as Y ₀ . (2) White Vaseline JIS K510 according to the Japanese Pharmacopoeia
Approximately 1 g of the pollutant obtained by kneading the pigment carbon black specified in 7 in a mass ratio of 10: 1 is applied to a cloth, and the surface of the test piece is rubbed by applying 5 reciprocating forces evenly in the vertical and horizontal directions to the contaminated part. after standing at room temperature it is covered with a watch glass for 30 minutes, cloth sufficient to wipe contaminants do the same operations and measurements (1), which is referred to as Y _1. (3) The contamination recovery rate (%) is the average value of the values obtained for three test pieces by the following formula.

[0059]

[Equation 1]

Here, Y (%) is the contamination recovery rate, Y ₁ is the diffuse reflectance after contamination cleaning, and Y ₀ is the diffuse reflectance before contamination.

Comparative Examples As silane monomer 1): Vinyltrimethylsilane (manufactured by Chisso Corporation) 2): Allyltrimethylsilane (manufactured by Chisso Corporation) 15): Vinyltrimethoxysilane (manufactured by Chisso Corporation) 16): Allyltri Methoxysilane (manufactured by Chisso Corporation) As a siloxane oligomer, 8): 1,3 bis (3-methacryloxypropyl) tetramethyldisiloxane (manufactured by Chisso Corporation) 14): 3-methacryloxypropyl pentamethyldisiloxane (Chisso) 17): 1,3-bis (3-methacryloxypropyl)
Tetrakis (trimethylsiloxy) disiloxane (manufactured by Chisso Corporation) 18): 3-methacryloxypropyl-bis (trimethylsiloxy) methylsilane (manufactured by Chisso Corporation), except that the formulation shown in Table 3 was changed. Then, a coating material was prepared and evaluated.

[0062]

[Table 1]

[0063]

[Table 2]

[0064]

[Table 3]

A: Poor adhesion of coating film (peeling of coating film during cutting) B: Impossible dispersion (poor dispersion of oligomer)

As is clear from Table 3, Comparative Examples 1, 5,
In 10 and 14, the contamination recovery rate is 86%, probably because the blending ratio of the silane monomer and the siloxane oligomer is too small.
It was low as below. Further, in Comparative Examples 2, 6, 11, and 15, since the blending ratio of the silane monomer and the siloxane oligomer was too high, poor adhesion of the coating layer or poor dispersion of the silane oligomer occurred.

Further, in Comparative Examples 3, 4, 12 and 13 using the silane monomer not satisfying the formula (1), the contamination recovery rate was lower than that of Comparative Example 18 containing no silane monomer. Further, in Comparative Examples 7, 8, 16 and 17 using siloxane not satisfying the formula (2), poor dispersion of the siloxane oligomer occurred.

On the other hand, as is clear from Tables 1 and 2, in Examples 1 to 38, the silane monomer satisfying the above formula (1) and the siloxane oligomer satisfying the formula (2) are within the scope of the present invention. Therefore, it is understood that the contamination recovery rate is as high as 95% or more, so that a molded article with a coating layer having excellent contamination recovery performance can be provided.

[0069]

When the coating material of the invention described in claim 1 is used, the low surface free energy of the specific silane monomer effectively enhances the hydrophobicity of the coating layer, so that the adhered dirt can be easily removed. It is possible to easily obtain a molded article having a coating layer having excellent stain recovery property.

Similarly, by using the coating material of the invention described in claim 2, since the hydrophobicity of the coating layer is effectively enhanced by the low surface free energy of the specific siloxane oligomer, the stain recovery property is excellent. A molded product having a coating layer can be easily obtained.

Therefore, according to the present invention, it is possible to provide a molded article with a coating layer capable of easily and surely removing dirt by wiping or the like even if dirt is attached to the surface by the in-mold coating molding method. It will be possible.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display location B29K 101: 10 105: 20 701: 10

Claims (2)

[Claims] 1. A thermosetting resin composition used as a coating material in an in-mold coating molding method in which a thermosetting coating material is coated and cured on the surface of a thermosetting molding material in a mold to form a coating layer. Therefore, the silane monomer represented by the following general formula (1) is used as a thermosetting resin component 1 containing a thermosetting resin and a copolymerizable monomer.
A thermosetting resin composition for in-mold coating molding, characterized in that 0.5 to 5.0 parts by weight is contained with respect to 00 parts by weight. [Chemical 1] (In the above formula (1), R _{1 to} R ₃ are independently of each other a phenyl group or an alkyl group having 1 to 10 carbon atoms, m is 0 or an integer of 1 to 10, and Y ₁ is an ethylenic double bond. Represents an atomic group.) 2. A thermosetting resin composition used as a coating material in an in-mold coating molding method in which a thermosetting coating material is coated and cured on the surface of a thermosetting molding material in a mold to form a coating layer. Then, the reactive siloxane oligomer represented by the following general formula (2) or (3) is added in an amount of 0.1 to 100 parts by weight of the thermosetting resin containing the thermosetting resin and the copolymerizable monomer.
A thermosetting resin composition for in-mold coating molding, which comprises 2.5 parts by weight. [Chemical 2] (In the formula (2), R _{4 to} R ₉ are independently an alkyl group having 1 to 6 carbon atoms or a phenyl group, Y ₂ is an atomic group having an ethylenic double bond, and Y ₃ is an ethylenic double bond. Atomic group having a bond or hydrogen, n is 0 or 1
5 is an integer, k is 0 or an integer of 1 to 10, and l is 0 or an integer of 1 to 5. ) [Chemical 3] (In the above formula (3), R ₁₀ and R ₁₇ are independent of each other, and a methylene chain having 2 to 5 carbon atoms and having a portion bonded by one phenylene group, R _{11 to} R ₁₆ are independent of each other. The above-mentioned alkyl group having 1 to 6 carbon atoms, Y ₄ and Y ₅ are atomic groups each having an ethylenic double bond independent of each other, and p represents 0 or an integer of 1 to 5.)