JP2022156006A - Thermosetting resin composition and resin molding - Google Patents

Abstract

To provide a thermosetting resin composition and a resin molding which have excellent appearance, mechanical properties, and antifouling properties against water scale.SOLUTION: The thermosetting resin composition contains: one or more thermosetting resins (A) selected from the group consisting of unsaturated polyester resins, (meth)acrylic resins and vinyl ester resins; a polyalkylene glycol (B); and a glass filler (C). Out of oxyalkylene units constituting the polyalkylene glycol (B), an oxyethylene unit accounts for 70-90 mass% and a C3 oxyalkylene unit accounts for 10-30 mass%. The blending ratio of the polyalkylene glycol (B) is 1-15 pts.mass and the blending ratio of the glass filler (C) is 200-350 pts.mass based on 100 pts.mass of the thermosetting resins (A).SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to a thermosetting resin composition having excellent appearance, mechanical properties and antifouling properties against limescale, and a resin molding.

Plumbing products such as bathtubs, kitchen counters, washstands, etc. are made of thermosetting resins containing resins such as unsaturated polyester, acrylic resins or vinyl ester resins and radically polymerizable monomers, fillers, low shrinkage agents, and curing agents. It is obtained by molding a thermosetting resin composition containing agents, pigments, and the like. When molding a bathtub, the thermosetting resin composition is blended with glass filler, calcium carbonate and aluminum hydroxide as fillers in order to improve mechanical properties.

Patent Literature 1 discloses a thermosetting resin composition containing a silicone compound having antifouling properties against limescale and a thermosetting resin. Further, Patent Document 2 discloses a thermosetting resin composition containing a fluorine-containing block copolymer having an antifouling property against limescale and a thermosetting resin.

JP-A-2003-82233 JP 2017-14481 A

In recent years, there has been an increasing demand for bathtubs that are transparent and have excellent appearance, and in order to improve the appearance, a large amount of glass filler is added. However, since the glass filler is hydrophilic, it has the problem that it is not possible to easily remove the adhered limescale stains. was enough.

An object of the present invention is to provide a thermosetting resin composition and a resin molding having excellent appearance, mechanical properties, and water stain resistance.

The present invention is as follows.
(1) Contains one or more thermosetting resins (A) selected from the group consisting of unsaturated polyester resins, (meth)acrylic resins and vinyl ester resins, polyalkylene glycol (B), and glass filler (C) A thermosetting resin composition that
Among the oxyalkylene units constituting the polyalkylene glycol (B), the oxyethylene unit is 70 to 90% by mass, and the oxyalkylene unit having 3 carbon atoms is 10 to 30% by mass,
With respect to 100 parts by mass of the thermosetting resin (A), the blending ratio of the polyalkylene glycol (B) is 1 to 15 parts by mass, and the blending ratio of the glass filler (C) is 200 to 350 parts by mass. A thermosetting resin composition characterized by a

(2) A resin molding obtained by curing the thermosetting resin composition of (1).

The present invention is a thermosetting resin that can produce a molded article having excellent appearance, mechanical properties, and stain resistance against water stains by adding a specific polyalkylene glycol to a thermosetting resin containing a glass filler. A resin composition can be provided.

The present invention will be described in more detail below.
<Thermosetting resin (A)>
The thermosetting resin of the present invention is a resin obtained by dissolving one or more polymers selected from the group consisting of unsaturated polyesters, (meth)acrylic copolymers and vinyl esters in radically polymerizable monomers.

(Unsaturated polyester resin)
The unsaturated polyester resin is a resin obtained by dissolving an unsaturated polyester obtained by esterifying a polyhydric alcohol and an unsaturated polyacid component in a radically polymerizable monomer.

Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 2-methyl-1,3-propanediol, 1,2-butanediol, 1,5-pentanediol, 1,6- Hexanediol, dialcohols such as 1,2-cyclohexanedimethanol; bisphenol A and bisphenol F, propylene oxide adducts or ethylene oxide adducts such as bisphenol S; 2,2-di(4-hydroxycyclohexyl)propane {hydrogenated Bisphenol A}, commercially available dihydric alcohols such as polyethylene glycol and polypropylene glycol; glycerin, trimethylolethane, trimethylolpropane, pentaerythritol and dipentaerythritol. The said polyhydric alcohol may be used individually and may be used in combination of 2 or more type.

Examples of the unsaturated polyvalent acid component include α,β-unsaturated polyvalent carboxylic acids and reactive derivatives thereof. Examples of α,β-unsaturated polyvalent carboxylic acids include maleic acid, fumaric acid, itaconic acid, citraconic acid, and chloromaleic acid. Examples of the reactive derivative include acid anhydrides such as maleic anhydride, itaconic anhydride, and chloromaleic anhydride; and lower alkyl esters of the unsaturated polycarboxylic acids. The unsaturated polyacid component may be used alone or in combination of two or more.

In addition, in the above esterification reaction, a saturated polyacid component can also be used as necessary. Examples of saturated polyacid components include aliphatic polycarboxylic acids such as succinic acid, adipic acid, sebacic acid and tetrahydrophthalic acid; halogenated phthalic acids such as chlorendic acid (heptic acid) and tetrabromophthalic acid; acids, acid anhydrides such as tetrahydrophthalic anhydride, hexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, succinic anhydride, chlorendic anhydride, trimellitic anhydride, and pyromellitic anhydride; dimethyl orthophthalate, dimethyl isophthalate, and lower alkyl esters such as dimethyl terephthalate. Aromatic polyvalent carboxylic acids such as orthophthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, trimellitic acid and pyromellitic acid can also be used. The saturated polyacid component may be used alone or in combination of two or more.

The conditions for the reaction in the esterification are not limited at all, but for example, the reaction is carried out under an inert gas atmosphere such as nitrogen at a reaction temperature of 140 to 230 ° C., if necessary, using a reaction catalyst. done using. Examples of the reaction catalyst include manganese acetate, dibutyltin oxide, stannous oxalate, zinc acetate, and cobalt acetate. The reaction catalyst may be used alone or in combination of two or more.

Examples of the radically polymerizable monomer in the unsaturated polyester resin include vinyl monomers such as styrene, vinyl toluene, α-methylstyrene, vinyl acetate, methyl methacrylate, and ethyl methacrylate; diallyl phthalate, diallyl isophthalate, Allyl monomers such as triallyl isocyanurate and diallyl tetrabromphthalate; phenoxyethyl acrylate, 1,6-hexanediol acrylate, trimethylolpropane triacrylate, 2-hydroxyethyl acrylate and the like. The radically polymerizable monomer may be used alone or in combination of two or more. Among these, styrene, vinyl toluene and the like are commonly used.

The proportion of the unsaturated polyester in the unsaturated polyester resin is preferably 30 to 90% by mass from the viewpoint of improving the mechanical properties of the resin molding.

((meth)acrylic resin)
The (meth)acrylic resin is a resin obtained by dissolving a (meth)acrylic copolymer in a radically polymerizable monomer, and is also called an acrylic syrup.

As the (meth)acrylic resin, a known (meth)acrylic copolymer obtained by radically polymerizing a (meth)acrylic acid ester monomer can be used. preferably 50% by mass or more in the polymer mixture). The other radically polymerizable monomer component copolymerizable with methyl methacrylate is not particularly limited, and includes the (meth)acrylic acid alkyl ester monomers other than methyl methacrylate, the other monomers, and the like.

Examples of the radical polymerizable monomer in the (meth)acrylic resin include alkylene glycol di(meth)acrylate, 1,3-propylene glycol di(meth)acrylate, and neopentyl glycol di(meth)acrylate. Polyfunctional compounds such as glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, divinylbenzene, allyl (meth)acrylate, diallyl phthalate, vinyl (meth)acrylate, and vinyl crotonate monomers of the same type. The radically polymerizable monomer may be used alone or in combination of two or more. The radically polymerizable monomers include, in addition to the polyfunctional monomers, the above-mentioned methyl methacrylate, the above-mentioned (meth)acrylic acid alkyl ester monomers, the above-mentioned other monomers, and the like. You can

The proportion of the (meth)acrylic copolymer in the (meth)acrylic resin is preferably 10 to 50% by mass from the viewpoint of improving the mechanical properties of the resin molding.

(vinyl ester resin)
The vinyl ester resin is a resin obtained by dissolving a vinyl ester in a radically polymerizable monomer. An epoxy resin having two or more glycidyl ether groups in one molecule is added with an α,β-unsaturated monocarboxylic acid. Obtained by reaction.

Examples of the epoxy resin having two or more glycidyl ether groups in one molecule include, for example, diglycidyl ethers of bisphenol A, bisphenol AD, bisphenol F and bisphenol S, their high molecular weight analogues, phenol novolac type polyglycidyl ethers, ter, cresol novolak-type polyglycidyl ethers, and the like. In addition, halogenated derivatives of these can also be used. The epoxy resins having two or more glycidyl ether groups in one molecule may be used alone or in combination of two or more.

Examples of the α,β-unsaturated monocarboxylic acids include unsaturated monocarboxylic acids derived from acrylic acid, methacrylic acid, crotonic acid, tiglic acid, cinnamic acid, acrylic acid and/or methacrylic acid. be done. The α,β-unsaturated monocarboxylic acids may be used alone or in combination of two or more.

In the addition reaction, the reaction conditions are not particularly limited. For example, the addition reaction is carried out at a reaction temperature of 80° C. to 140° C. using a reaction catalyst if necessary. Examples of the reaction catalyst include tertiary amines such as benzyldimethylamine, triethylamine, N,N-dimethylaniline, triethylenediamine, and 2,4,6-tris(dimethylaminomethyl)phenol; quaternary ammonium salts; and metal salts such as lithium chloride. The reaction catalyst may be used alone or in combination of two or more.

Examples of the radically polymerizable monomer in the vinyl ester resin include vinyl monomers such as styrene, vinyl toluene, α-methylstyrene, vinyl acetate, methyl methacrylate, and ethyl methacrylate; allyl monomers such as allyl isocyanurate and diallyl tetrabromphthalate; phenoxyethyl acrylate, 1,6-hexanediol acrylate, trimethylolpropane triacrylate, 2-hydroxyethyl acrylate and the like; The radically polymerizable monomer may be used alone or in combination of two or more. Among these, styrene, vinyl toluene and the like are commonly used.

The proportion of the vinyl ester in the vinyl ester resin is preferably 10 to 50% by mass from the viewpoint of improving the mechanical properties of the resin molding.

<Polyalkylene glycol (B)>
Polyalkylene glycol has oxyethylene units and oxyalkylene units having 3 carbon atoms. The arrangement of the oxyethylene units and the oxyalkylene units having 3 carbon atoms is preferably block-like. A block-shaped polyalkylene glycol is usually represented by the following general formula (1).

HO—(C ₂ H ₄ O) _a —(C ₃ H ₆ O) _b —(C ₂ H ₄ O) _a —H (1)

Polyalkylene glycol may be used alone or in combination of two or more.
The weight average molecular weight of the polyalkylene glycol (B) is preferably 3,000 to 25,000, more preferably 10,000 to 20,000, from the viewpoint of improving antifouling properties.

When the total ratio of oxyalkylene units in the polyalkylene glycol (B) is 100% by mass, the ratio of oxyethylene units is 70 to 90% by mass, and the ratio of oxyalkylene units having 3 carbon atoms is 10 to 30% by mass. is. The ratio of oxyethylene units is more preferably 75 to 90% by mass, and the ratio of oxyalkylene units having 3 carbon atoms is more preferably 10 to 25% by mass.

The blending amount of the polyalkylene glycol (B) is 1 to 15 parts by mass with respect to 100 parts by mass of the thermosetting resin (A), preferably 3 to 13 parts by mass, more preferably 5 to 13 parts by mass. 7 to 11 parts by mass are particularly preferred.

<Glass filler (C)>
The glass filler (C) of the present invention is not particularly limited, but from the viewpoint of improving the workability and mechanical properties of mixing the components constituting the thermosetting resin composition, several thousand glass fibers are bundled. A chopped strand obtained by cutting a strand to a length of 3 to 25 mm, or a milled fiber obtained by grinding a single fiber to a length of several tens to several hundred μm is preferable.

From the viewpoint of improving the appearance of the resin molded product, when an unsaturated polyester resin is used as the thermosetting resin, the refractive index nD is preferably 1.54 to 1.58. When using an acrylic resin, the refractive index nD is preferably 1.48 to 1.52, and when using a vinyl ester resin as a thermosetting resin, the refractive index nD is 1.49 to 1.57. is preferred.

The blending amount of the glass filler (C) is 200 to 350 parts by mass with respect to 100 parts by mass of the thermosetting resin (A). 220 to 330 parts by mass is preferable, and 250 to 300 parts by mass is more preferable.

<Other additives>
Other additives generally used in thermosetting resin compositions can be used in the thermosetting resin composition of the present invention. Examples of the other additives include curing agents, curing accelerators, retarders, thickeners, low shrinkage agents, internal release agents, dyes, pigments, ultraviolet absorbers, antioxidants, and the like.

Examples of the curing agent include known organic peroxides such as ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxydicarbonates, and peroxyesters. The curing agent is usually used in an amount of about 0.1 to 5 parts by mass with respect to 100 parts by mass of the thermosetting resin (A).

Further, when using the curing agent, tertiary amines such as N,N-dibutylaniline and tributylamine; acetoacetic esters such as ethyl acetoacetate and propyl acetoacetate; cobalt salts such as cobalt naphthenate and cobalt octylate; A curing accelerator such as can be used. The curing accelerator is usually used in an amount of about 0.01 to 0.5 parts by mass with respect to 100 parts by mass of the curing agent.

Examples of the retarder include hydroquinones such as hydroquinone, methylhydroquinone, 2-methylhydroquinone and t-butylhydroquinone; benzoquinones such as p-benzoquinone and methyl-p-benzoquinone; catechols such as catechol and t-butylcatechol. system; phenolic such as 2,6-di-t-butyl-4-methylphenol, 4-methoxyphenol, cresol; N such as 1-oxyl-2,2,6,6-tetramethylpiperidin-4-ol - Known retarders such as oxyl-based. The retarder is usually used in an amount of about 0.01 to 1 part by mass with respect to 100 parts by mass of the thermosetting resin (A).

Examples of the thickener include magnesium oxide, magnesium hydroxide, calcium hydroxide and the like. The thickener is usually used in an amount of about 0.5 to 5 parts by mass with respect to 100 parts by mass of the thermosetting resin (A).

Examples of the internal release agent include wax, polyvinyl alcohol solution, silicone-based release agent, zinc stearate, calcium stearate, and the like. The internal release agent is usually used in an amount of about 1 to 10 parts by mass with respect to 100 parts by mass of the curable resin (A).

<Resin molding>
The resin molded article of the present invention is obtained by curing (molding) the thermosetting resin composition. The curing (molding) can be performed with the thermosetting resin composition alone, or can be performed with a composite material so as to cover the surface or the entire article.

The method for curing (molding) the thermosetting resin composition is not particularly limited, but examples include hand lay-up molding, spray-up molding, filament winding molding, resin injection molding, bulk molding compound ( BMC) press method, sheet molding compound (SMC) press method, resin transfer molding (RTM) method, molding method for manufacturing FRP products such as corrugated sheet/flat continuous molding method, pultrusion molding method, vacuum molding method, Air pressure molding, compression molding, injection molding, casting, spraying, gel coating, lining, flow coating and the like can be mentioned. The curing (molding) temperature is about 70 to 180° C., and the curing time is about 0.5 to 60 minutes.

The resin molded article of the present invention is suitable for plumbing members. Examples of plumbing members include members used in bathrooms such as bathtubs, unit baths, shower heads, shower bars, handrails, bathroom walls, bathroom floors, and bathroom doors, kitchen counters, washstands, and the like.

EXAMPLES The present invention will be described below with reference to Examples, but the present invention is not limited to the following.
<Production of thermosetting resin composition>
Each component shown in Tables 1 and 2 is blended, and in addition, 2.0 parts by mass of t-butyl peroxyisopropyl carbonate as a curing agent per 100 parts by mass of the thermosetting resin (A) (manufactured by NOF Corporation, trade name: Perbutyl I-75), 0.05 parts by mass of parabenzoquinone as a retarder, 5.0 parts by mass of zinc stearate as an internal release agent, and a thickener. 2.0 parts by mass of magnesium oxide was added to each. Each obtained formulation was mixed for 15 minutes in a kneader to obtain a thermosetting resin composition.

<Production of resin molding>
The resulting thermosetting resin composition was wrapped in a sheet with a polyethylene terephthalate film and left in an atmosphere of 40° C. for 24 hours to prepare a preform. Using a 100-ton press, the obtained preform was compression molded for 4 minutes at a mold temperature of 140° C./145° C. (lower mold/upper mold) and a molding pressure of 10 MPa to obtain a flat plate of 150 mm×100 mm×4 mm. A resin molding was obtained.

The evaluation method for each performance is as follows.
<Appearance (Glossiness)>
For evaluation of glossiness, the test piece obtained above was used, 60° specular glossiness was measured according to JIS K7105, and the change rate (%) of glossiness was calculated by the following formula.

Glossiness change rate (%) =
{(Glossiness of test piece) / (Glossiness of test piece (equivalent to blank) containing no polyalkylene glycol (B))} × 100

A gloss evaluation result of 90 or more was considered acceptable.

<Mechanical properties (bending strength)>
Bending strength was measured at 23° C. and a bending speed of 2 mm/min according to JIS K 7203. A bending strength of 200 MPa or more was considered acceptable.

<Anti-fouling property against limescale>
The Si standard solution for atomic absorption measurement was diluted so that the Si concentration was 100 ppm, and 0.06 g of this was dropped on the surface of the test piece obtained above and evaporated in a dryer at 50 ° C., An operation of dropping 0.06 g onto the same place again and completely evaporating at 50° C. was repeated 10 times. Next, wipe off with water-moistened gauze, and drop 0.06 g of a methylene blue solution having a concentration of 10 μmol/L to the spot where the water was dropped to dye the limescale blue, thereby measuring the color difference ΔE between before and after the drop. did. A color difference meter "CR-400" manufactured by Konica Minolta was used.
Regarding the antifouling property against limescale of each resin molding, the evaluation score was calculated according to the following criteria. As for the antifouling property against limescale, 4 or more was regarded as a pass.

5: ΔE is less than 0.1 4: ΔE is 0.1 or more and less than 0.2 3: ΔE is 0.2 or more and less than 0.3 2: ΔE is 0.3 or more and less than 0.5 1: ΔE is 0.0. 5 or more

The following components were used for each component in Tables 1 and 2.
A-1: Unsaturated polyester resin; manufactured by Japan U-Pica Co., Ltd., 7579
A-2: (meth) acrylic resin; manufactured by Japan U-Pica Co., Ltd., 8932
A-3: Vinyl ester resin; manufactured by Japan U-Pica Co., Ltd., 8101
B-1 to B-4 and B'-1, B'-2:
HO—(C ₂ H ₄ O) _a —(C ₃ H ₆ O) _b —(C ₂ H ₄ O) _a —H using formula (1) (1)
However, the molecular weight Mw and the ratio of oxyethylene units and oxyalkylene units having 3 carbon atoms are shown in Tables 1 and 2.
C: Chopped strand; made by Nippon Sheet Glass, RES03-BM5
S-1: Silicone compound; manufactured by Shin-Etsu Silicone Co., Ltd., KF96
F-1: fluorine-containing block copolymer

<Synthesis of F-1>
A 5-liter four-necked flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 600 g of methyl ethyl ketone and heated to 70° C. while nitrogen gas was blown thereinto. After that, a mixture of 253 g of methyl methacrylate (MMA) and 247 g of butyl methacrylate (BMA) and a mixture of 400 g of methyl ethyl ketone and 110 g of polymeric peroxide were simultaneously charged over 2 hours, and the polymerization reaction was continued for 4 hours. gone. As a result, dispersions of MMA and BMA polymers constituting non-fluorine segments were obtained.

Subsequently, a mixture of 850 g of methyl ethyl ketone, 317 g of fluorine monomer CH ₂ =CHCOO(CH ₂ ) ₂ (CF ₂ ) ₅ CF ₃ <FA(C ₆ )>, and 17 g of methyl methacrylate (MMA) was added over 40 minutes. After charging, the polymerization reaction was carried out for 1.5 hours. Furthermore, F-1 (Mw=40000) was obtained by performing a polymerization reaction at 80° C. for 3 hours.

As is clear from the results in Table 1, Examples 1 to 10 were all excellent in appearance, mechanical properties, and antifouling properties.

On the other hand, as is clear from Table 2, Comparative Examples 1 to 5 had an insufficient balance of these properties.
Specifically, in Comparative Example 1, the amount of the oxyethylene unit blended in the polyalkylene glycol (B'-1) was too small, so the antifouling property against limescale was poor.
Comparative Example 2 was inferior in antifouling property against limescale due to the excessive content of oxyethylene units in the polyalkylene glycol (B'-2).
Comparative Example 3 was inferior in mechanical properties because the blending amount of the glass filler (C) was too small.
In Comparative Example 4, a silicone compound was blended instead of the polyalkylene glycol (B), so the antifouling property against limescale was inferior.
In Comparative Example 5, the fluorine-containing block copolymer was blended instead of the polyalkylene glycol (B), so the antifouling property against limescale was inferior.

Claims (2)

Thermosetting containing one or more thermosetting resins (A) selected from the group consisting of unsaturated polyester resins, (meth)acrylic resins and vinyl ester resins, polyalkylene glycol (B), and glass fillers (C) a flexible resin composition,
Among the oxyalkylene units constituting the polyalkylene glycol (B), the oxyethylene unit is 70 to 90% by mass, and the oxyalkylene unit having 3 carbon atoms is 10 to 30% by mass,
With respect to 100 parts by mass of the thermosetting resin (A), the blending ratio of the polyalkylene glycol (B) is 1 to 15 parts by mass, and the blending ratio of the glass filler (C) is 200 to 350 parts by mass. A thermosetting resin composition characterized by a
A resin molded article obtained by curing the thermosetting resin composition according to claim 1 .