JP2002120788A - Hull made of unsaturated polyester resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hull made of synthetic resin constituted by unsaturated polyester resin composition by which weather resistant gloss keeping efficiency and discoloration resistance are improved and having a small amount of polymerizable unsaturated monomer. SOLUTION: The hull made of synthetic resin comprises unsaturated polyester resin composition which includes unsaturated polyester and polymerizable unsaturated monomer, and a cured article thereof exhibits gloss keeping efficiency of 60% or more (gloss keeping efficiency after 2,000 hours passed after weather resistance test by a sunshine weather meter based on ISO standard).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a synthetic resin hull made of an unsaturated polyester resin composition having excellent gloss retention and yellowing resistance and having a low polymerizable unsaturated monomer content.

[0002]

2. Description of the Related Art Unsaturated polyester resins have been used in various applications because of their excellent moldability, chemical, physical, mechanical, and electrical properties in which the curing temperature conditions are wide and the curing speed is fast. Ships are one of their main uses. On the other hand, one of the performances required to improve the unsaturated polyester resin is weather resistance. This performance improvement is addressed by the raw material composition and other methods.

[0003] In other words, from the viewpoint of raw material composition, use of alicyclic aliphatic dibasic acids, glycols, or neopentyl glycol, and addition of various ultraviolet absorbers, and the like. However, although the discoloration such as yellowing is improved by the improvement of the raw material composition, the gloss retention still has a defect. In other words, there is a problem that a decrease in gloss, such as chalking (a whitening phenomenon such as dusting the surface as a result of the decrease in gloss), occurs in a relatively short time,
Neither discoloration such as yellowing, which is a factor of weather resistance, nor gloss retention was satisfied.

[0004] Also, recently, due to environmental problems, regulations on the release of styrene monomer into the atmosphere have been becoming stricter, so that resins having low styrene volatilization and low styrene content are required. In order to obtain an unsaturated polyester resin having a low styrene volatilization or a low styrene content, a method of reducing the styrene content by using a low molecular weight unsaturated polyester of DCPD type, a method of adding a paraffin wax, and the like are known. These methods can reduce the volatilization amount and content of the styrene monomer, but cannot satisfy the weather resistance.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a synthetic polyester resin composition comprising an unsaturated polyester resin composition having both improved weather resistance gloss retention and discoloration resistance, and having a low polymerizable unsaturated monomer content. An object of the present invention is to provide a resin hull.

[0006]

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have conducted intensive studies on unsaturated polyester resin compositions. The inventors have found an unsaturated polyester resin composition having a low unsaturated monomer content, and have confirmed that a hull can be formed using the same, thereby completing the present invention.

That is, the present invention provides: (A) An unsaturated polyester and (B) a polymerizable unsaturated monomer, and the cured product has a gloss retention (after 2000 hours of a weathering test with a sunshine weatherometer based on ISO standards). Gloss retention) is 6
A hull made of a synthetic resin, comprising an unsaturated polyester resin composition having 0% or more,

[0008] 2. 2. The synthetic resin hull according to the above 1, wherein the cured product has a hot-cold shrinkage stress at 70 ° C to 20 ° C of 17 MPa or less.

3. 3. The synthetic resin hull according to the above item 2, wherein the cured product has a heat / cold shrinkage stress / maximum elastic strength of 1 or less.

[0010] 4. Color difference in cured product (color difference ΔE of 3 mm thick test piece after 2000 hours of weathering test by sunshine weatherometer based on ISO standard)
Is 1 or 2 or 3 or less.
The hull made of synthetic resin described in

5. A composition comprising (A) an unsaturated polyester and (B) a polymerizable unsaturated monomer,
(A) / (B) = 70 / 30-95 / 5 by weight ratio of (A) unsaturated polyester to (B) polymerizable unsaturated monomer. The synthetic resin hull described in Crab,

6. (B) The synthetic resin hull according to any one of (1) to (5) above, wherein the polymerizable unsaturated monomer is mainly composed of a styrene monomer and an acrylic monomer.

7. The weight ratio of (A) the unsaturated polyester to (B) the polymerizable unsaturated monomer having a styrene monomer and an acrylic monomer as main components is 5 to 95% of the unsaturated polyester, and the styrene monomer is The hull made of synthetic resin according to 6 above, wherein the hull is composed of 1 to 30% of a monomer and 4 to 65% of an acrylic monomer.

8. The synthetic resin hull according to any one of the above 1 to 7, which comprises an ultraviolet absorber and / or an ultraviolet stabilizer,

9. A synthetic resin hull having a colored surface layer made of the resin composition of the above 1 to 8 and a synthetic resin base layer,

10. 10. The synthetic resin hull according to the above 9, wherein the synthetic resin base layer comprises the resin composition according to any one of the above 1 to 8 containing a reinforcing material.

[0017]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.

The unsaturated polyester used in the present invention may be an unsaturated dibasic acid and / or an acid anhydride and / or an aromatic dicarboxylic acid and / or an acid anhydride thereof, and / or an aliphatic dicarboxylic acid and / or The acid component containing the acid anhydride and / or the alicyclic aliphatic dicarboxylic acid and / or the acid anhydride and / or the aliphatic carboxylic acid and / or the aromatic carboxylic acid, and the polyhydric alcohol are known. Is an unsaturated polyester obtained by the reaction according to the above method. An unsaturated polyester acrylate obtained by adding, for example, an unsaturated epoxy compound or an unsaturated isocyanate compound to the terminal of the polyester may be used. Further, the terminal may be blocked with dicyclopentadiene.

Examples of the acid component and alcohol for the condensation reaction of the unsaturated polyester used in the present invention are shown below, but are not limited thereto.

Examples of unsaturated dibasic acids and / or anhydrides thereof include maleic acid, maleic anhydride, fumaric acid,
Α, β such as itaconic acid, citraconic acid, aconitic acid
Β, γ-unsaturated dibasic acids such as unsaturated dibasic acids and dihydromuconic acids are used. These may be used in combination of two or more. Among these, maleic acid, maleic anhydride,
Fumaric acid is preferred because it is readily available. Aromatic dicarboxylic acids and / or acid anhydrides thereof include phthalic anhydride, isophthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid,
3-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic anhydride, 4,4′-biphenyldicarboxylic acid,
Trimet acid, pyromellitic acid and the like. These halides; and their ester derivatives are also used. These may be used in combination of two or more.

Examples include tetrahydrophthalic anhydride and dimer acid. Aliphatic dicarboxylic acids and / or acid anhydrides thereof include oxalic acid, malonic acid, succinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, hexylsuccinic acid, adipic acid, sebacic acid , Azelaic acid, glutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3,3-diethylglutaric acid, pimelic acid, suberic acid, dodecane And diacids. These halides; and their ester derivatives are also used. These may be used in combination of two or more.

The cycloaliphatic aliphatic dicarboxylic acids and / or acid anhydrides thereof include hexahydrophthalic anhydride, hexahydrophthalic acid, 1,4-cyclohexanedicarboxylic acid,
For example, 1,3-cyclohexanedicarboxylic acid, methylhexahydrophthalic anhydride, methylhexahydrophthalic acid, hexic acid, 1,1-cyclobutanedicarboxylic acid and the like are used. These halides; and their ester derivatives are also used. These may be used in combination of two or more.

The aliphatic carboxylic acid includes cyclohexanecarboxylic acid, lactic acid, malic acid, tartaric acid, citric acid and the like, and these may be used in combination of two or more. Examples of the aromatic carboxylic acid include benzoic acid, and these may be used in combination of two or more. The acid component is appropriately selected from these, but in order to obtain a resin composition having excellent yellowing resistance, an acid other than an aromatic compound such as an aromatic monocarboxylic acid, an aromatic dicarboxylic acid or an anhydride thereof is used. It is preferred to use components.

Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4 -Butanediol, 2,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10- Decanediol, 4,5-nonanediol, neopentyl glycol, 2-butyl-
2-ethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 1,4-cyclohexanedimethanol, 1,2-cyclohexanediol,
1,3-cyclohexanediol, 1,4-cyclohexanediol, 2-methyl-1,4-butanediol,
2-ethyl-1,4-butanediol, 2-methyl-
1,3-propanediol, 3-methyl-1,5-pentanediol,

Adducts of hydrogenated bisphenol A, hydrogenated bisphenol A with an alkylene oxide such as ethylene oxide, propylene oxide or butylene oxide, and alkylenes of bisphenol A such as ethylene oxide or propylene oxide or butylene oxide Adducts with oxides, hydrogenated bisphenol F, adducts of hydrogenated bisphenol F with alkylene oxides such as ethylene oxide or propylene oxide or butylene oxide,
Adducts of bisphenol F with alkylene oxides such as ethylene oxide or propylene oxide or butylene oxide; dihydric alcohols such as ethylene glycol carbonate; trihydric alcohols such as glycerin and trimethylolpropane; pentaerythritol Is used.

These may be used in combination of two or more, and are appropriately selected. In order to obtain a resin composition having excellent yellowing resistance, an aromatic compound which causes yellowing, that is, a chromophore formed by a photoreaction is used. It is preferable not to use a compound such as an aromatic compound or an ether bond, which easily undergoes a deterioration reaction by light. Further, when a polymer such as 1,3-propanediol or 2-butyl-2-ethyl-1,3-propanediol has an odd-numbered carbon atom in the main chain and uses a low-melting alcohol. There is an advantage that the content of the polymerizable unsaturated monomer can be reduced and the viscosity of the obtained composition can be reduced. That is, an alcohol having an odd-numbered carbon atom in the main chain is more preferable because the viscosity of the resin becomes lower.

Furthermore, since synthetic resin hulls are often used at sea, such as fishing boats and pleasure boats, it is better to use an alcohol which is not easily hydrolyzed, such as neopentyl glycol, for better salt water resistance and hydrolysis resistance. Therefore, it is more preferable to use a vinyl ester resin containing no benzene ring in combination with the unsaturated polyester resin having the above physical properties to make a composition excellent in salt damage.

For blocking the terminals of the unsaturated polyester, monohydric alcohols such as benzyl alcohol, 2-ethylhexyl alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol, tridecyl alcohol, and stearyl alcohol can also be used.

The reaction between the acid component and the polyhydric alcohol is carried out mainly by advancing a condensation reaction by a known method, and a low molecule such as water generated when both components react is desorbed out of the system and allowed to proceed. . There is no particular limitation on the reaction ratio between the acid component and the polyhydric alcohol. It may be reacted with an unsaturated epoxy compound at a stage having a carboxyl group at the terminal, or may be reacted with an unsaturated compound having an isocyanate group or an unsaturated carboxylic acid or an acid anhydride thereof at a stage having a hydroxyl group at a terminal. . Further, dicyclopentadiene is first reacted with maleic anhydride, alcohol or water under ordinary esterification reaction conditions, and if necessary, aliphatic saturated mono- or dibasic acids and / or acid anhydrides and unsaturated di- or di-basic acids. A basic acid and / or an acid anhydride thereof, an aromatic dicarboxylic acid and / or an acid anhydride thereof may be added, and a condensation reaction may be performed by a known method.

The method of adding an unsaturated epoxy compound such as glycidyl methacrylate to the terminal carboxyl group is not particularly limited, but may be 60 to 200 with a quaternary ammonium salt, a metal soap, various amines or the like as a catalyst.
The reaction can be carried out at 0.5 ° C. for 0.5 to 4 hours. The addition reaction includes a method of dissolving the unsaturated polyester in the polymerizable unsaturated monomer and then adding the unsaturated epoxy compound, and a method of directly adding the unsaturated epoxy compound to the unsaturated polyester. A method may be adopted.

The method of adding the unsaturated compound having an isocyanate group to the terminal hydroxyl group is not particularly limited, but if necessary, a reaction catalyst may be added and the mixture may be added at 60 to 200 ° C. for 0.5 hour.
The reaction can be carried out for up to 8 hours. The addition reaction is a method in which a diisocyanate is added to an unsaturated polyester to react an ethylenically unsaturated monomer having a hydroxyl group, and a method in which an adduct of a diisocyanate and an ethylenically unsaturated monomer having a hydroxyl group is added to the unsaturated polyester. And a method of adding an isocyanate having an ethylenically unsaturated monomer to an unsaturated polyester, etc., and any method may be employed. The addition reaction includes a method of dissolving the unsaturated polyester in the polymerizable unsaturated monomer and then adding the unsaturated isocyanate compound, and a method of directly adding the unsaturated isocyanate compound to the unsaturated polyester. A method may be adopted.

Examples of the diisocyanate compound include hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, and tetramethyl xylylene diisocyanate.
Examples of the ethylenically unsaturated monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate and (meth) acrylate.
2-hydroxypropyl acrylate, 3-hydroxypropyl (meth) acrylate and the like can be mentioned. As unsaturated isocyanate compounds, isopropenyldimethylbenzyl isocyanate, Karenz MOI (Showa Denko KK)
Manufactured).

The method for reacting an unsaturated carboxylic acid such as (meth) acrylic acid or di (meth) acrylic anhydride or an acid anhydride thereof with a terminal hydroxyl group is not particularly limited,
The reaction can be carried out at 60 to 200 ° C. for 0.5 to 4 hours using a known esterification and / or transesterification catalyst. The reaction may be performed under reduced pressure.
For the reaction, after dissolving the unsaturated polyester in the polymerizable unsaturated monomer, a method of reacting the unsaturated carboxylic acid or its anhydride with the unsaturated carboxylic acid or the anhydride thereof directly with the unsaturated polyester is used. There is a way to make it react,
Either method may be adopted.

As the polymerizable unsaturated monomer, one in the molecule is used.
Styrene derivatives having at least two polymerizable double bonds, such as styrene, p-methylstyrene, α-methylstyrene, t-butylstyrene, vinyltoluene, divinylbenzene, chlorostyrene and dichlorostyrene, monomethyl fumarate and fumaric acid Dimethyl, monomethyl maleate,
Dimethyl maleate, monoethyl fumarate, diethyl fumarate, monoethyl maleate, diethyl maleate,
Monopropyl fumarate, dipropyl fumarate, monopropyl maleate, dipropyl maleate, monobutyl fumarate, dibutyl fumarate, monooctyl fumarate, dioctyl fumarate, monomethyl itaconate, dimethyl itaconate, diethyl itaconate, monoethyl itaconate , Α, β such as monobutyl itaconate, dibutyl itaconate, monopropyl itaconate and dipropyl itaconate
-Unsaturated polybasic acid alkyl esters, diallyl phthalate and the like are used. These may be used in combination of two or more.

Examples of the acrylic monomer include (meth) acrylic monomers such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, and methacrylic acid. Lauryl, propyl methacrylate, isopropyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, dicyclopentenyloxyethyl methacrylate, t-butyl Methacrylic acid such as cyclohexyl methacrylate and methacrylic acid and esters thereof,

Methyl acrylate, ethyl acrylate, butyl acrylate, propyl acrylate, isopropyl acrylate, 2-ethylhexyl acrylate, laurel acrylate, 2-hydroxyethyl acrylate, cyclohexyl acrylate, isobornyl acrylate, dicyclo Acrylic acid such as pentenyloxyethyl acrylate, t-butylcyclohexyl acrylate, acrylic acid and its esters, (meth) acrylamide, methoxydiethylene glycol (meth) acrylate, methoxytetraethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) ) Acrylate,

Β- (meth) acryloyloxyethyl hydrogen phthalate, β- (meth) acryloyloxypropyl hydrogen phthalate, β- (meth) acryloyloxyethyl hydrogen succinate, nonylphenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) Acrylate, phenoxy polyethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate,
Butoxydiethylene glycol (meth) acrylate,
Nonylphenoxyethyl (meth) acrylate and the like can be mentioned. These may be used in combination of two or more.

Also, for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate ,
Propylene glycol di (meth) acrylate, 1,4-butylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, tri Methylolpropane tri (meth) acrylate,

Trimethylolethanetri (meth) acrylate, tetramethylolmethanetri (meth) acrylate, tetramethylolethanetri (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, 2,2-bis [4-((meth ) Acryloxyethoxy)
Phenyl] propane, pentaerythritol tri (meth) acrylate, cipentaerythritol hexa (meth) acrylate, oligoester (meth) acrylate, urethane (meth) acrylate oligomer, (meth) acryl-modified epoxy oligomer, epoxy-modified acrylic urethane oligomer, ( A (meth) acrylate oligomer can also be mentioned. These may be used in combination of two or more.

The compounding amount of the polymerizable unsaturated monomer is preferably such that the weight ratio of (A) the unsaturated polyester to (B) the polymerizable unsaturated monomer is (A) / (B) = 70/30. ~ 95 /
5, more preferably 70/30 to 85/15. Alternatively, when the polymerizable unsaturated monomer (B) is mainly composed of a styrene monomer and an acrylic monomer, (A) an unsaturated polyester and (B) a styrene monomer and The weight ratio of the polymerizable unsaturated monomer having an acrylic monomer as a main component to the unsaturated polyester 5
９５95%, styrene monomer 1-30% and acrylic monomer 4４65%. If the amount of the polymerizable unsaturated monomer is in the above range, it has a good effect on the high gloss retention of the cured product of the composition, and the polymerizable unsaturated monomer, for example, low volatility of styrene, low content. Can be brought.

The composition of the present invention has a viscosity of 4.5 to 4.5.
It is preferably adjusted to 0.2 Pa · s,
It is more preferable that the polymer has thixotropy and the thixotropy does not change with the storage period.

Examples of the ultraviolet absorber include benzophenone-based, benzotriazole-based, and cyanoacrylate-based compounds, and examples of the ultraviolet stabilizer include hindered amine-based compounds. Regardless of the form, they may have a polymerizable reactivity or an esterification-reactive reactivity, and are appropriately selected and used.

The unsaturated polyester resin composition of the present invention may contain, if necessary, hydroquinone, pyrocatechol,
Polymerization inhibitors such as 2,6-t-butylparacresol; metal soaps such as cobalt naphthenate and cobalt octenoate; quaternary ammonium salts such as dimethylbenzylammonium chloride; β diketones such as acetylacetone; dimethylaniline; -Ethyl-meta toluidine,
Various additives such as curing accelerators such as amines such as triethanolamine, dyes, pigments, plasticizers, known thixotropic agents such as silica powder and asbestos powder, fillers, stabilizers, defoamers, and leveling agents. A thermoplastic polymer such as PMMA or a macromonomer AA-6 or AA-10 from Toagosei Chemical Industry Co., Ltd. can be blended within a range that does not impair the gloss retention performance.

The resin composition may contain various organic peroxides as a curing agent. Examples of the organic peroxide include methyl ethyl ketone peroxide, benzoyl peroxide, acetylacetone peroxide, bis-4-t-butylcyclohexanedicarbonate, t-
Butyl peroxy-2-ethyl hexanate and the like,
These may be used in combination of two or more.

The pigment used in the present invention is preferably used for coloring, for example, titanium white,
Vengara, condensed azo red, titanium yellow, cobalt blue, quinacridone red, carbon black,
Iron black, ultramarine green, blue, perinone, navy blue, isoindolinone, chrome green, cyanine blue, green and the like. Excellent UV stability,
A material that does not hinder the curing of the polyester resin is selected and blended according to the color tone. These coloring pigments can be directly mixed and dispersed in the polyester resin or added as a color toner which has been previously kneaded with a saturated or unsaturated polyester resin solid. The amount of the pigment added is determined by dissolving the unsaturated polyester and the polymerizable unsaturated monomer.
The pigment is preferably used in an amount of 0.1 to 50 parts by weight based on 00 parts by weight.

The filler used in the composition of the present invention includes, for example, calcium carbonate, talc, mica, clay, silica powder, colloidal silica, asbestos powder, barium sulfate, aluminum hydroxide, glass powder, alumina powder, silica powder Powder, glass beads, crushed sand and the like can be mentioned.

The composition containing the unsaturated polyester and the polymerizable unsaturated monomer of the present invention as the main components has a gloss retention of a cured product having a thickness of 3 mm (a sunshashin wafer based on the ISO standard). (A gloss retention after 2000 hours of a weather resistance test by a zometer) is 60% or more, preferably 70% or more, and the cured product has a hot-cold shrinkage stress at 70 ° C to 20 ° C of 17 MPa or less, preferably 15 MPa or less; It has a color difference (ΔE) of 20 or less, preferably 16 or less, and also has a physical property value of hot-cold shrinkage stress / maximum elastic strength of 1 or less, preferably 0.05 or more and 0.85 or less. is there.

The above-mentioned hot-cold shrinkage stress in the present invention is measured as follows. First, the unsaturated polyester resin composition is applied on a glass plate so that the thickness of the cured film becomes about 0.3 mm, and left at room temperature for 24 hours to prepare a cured film. 70 mm of the obtained film
Attach × 10 mm × about 0.3 mm to Tensilon and heat it to Tg or more of the film. The cured film is stretched and loosened, but the sample length is increased and fixed by the amount of this looseness, and the generated stress is measured while lowering the temperature.
The difference between the generated stresses at a temperature of 70 ° C is defined as a hot-cold shrinkage stress of 70 ° C to 20 ° C. In addition, within the above-mentioned range of the heat-cold shrinkage stress, it is effective to maintain the gloss of the cured product, and it can also impart a property of preventing cracking caused by a temperature change when the formed boat is used.

The maximum elastic strength in the present invention is measured as follows. In the same manner as in the preparation for the measurement of the thermal shrinkage stress, the unsaturated polyester resin composition was applied on a glass plate so that the thickness of the cured film became about 0.3 mm, and left at room temperature for 24 hours. For 30 minutes to produce a cured film. 70 mm × 10 mm × about 0.3 mm of the obtained film was attached to Tensilon and measured at a room temperature at a test speed of 5 mm / min.

In the initial stage of the strain-stress curve, the strength is determined from the maximum stress in a region according to the linear equation, and the strength is defined as the maximum elastic strength, and the ratio of the hot-cold shrinkage stress / maximum elastic strength is determined. In addition, if it is in the range of the above-mentioned hot-cold shrinkage stress / maximum elastic strength, it is effective in maintaining gloss of a cured product, and has mechanical strength effective in a wide range of applications when used as a coating material or a molded product. The property of preventing the number of temperature changes, that is, cracks caused by fatigue, can also be provided.

The gloss retention and color difference in the present invention are measured as follows. A spacer for adding 1.0% of 55% methyl ethyl ketone peroxide and 0.1% of 6% cobalt naphthenate to the unsaturated polyester resin composition, stirring, defoaming, applying a release agent, and adjusting the thickness to 3 mm. The resin is poured into a sealed glass plate having the following, and then left at room temperature for 24 hours.
It is further cured to obtain a casting plate having a thickness of about 3 mm. A test piece of 75 mm × 70 mm was cut out from the test plate thus obtained to prepare a weathering test piece. As a weather resistance test method, an accelerated weather resistance test was performed using a sunshine weatherometer based on the ISO standard. The gloss retention rate is
The specular glossiness is measured at an incident angle of 60 degrees by a method based on JIS Z8741-1997. The gloss retention is determined by the following equation.

Gloss retention = mirror gloss after weathering test / mirror gloss before weathering test × 100 This indicates that the higher the gloss retention, the lower the gloss is.

The color difference is in accordance with JIS Z 8730-1995.
Use the notation specified in. JIS Z for object color
Measured according to the method specified in 8722 and L ^* a ^* b ^*
The color difference according to the color system is calculated by the following equation (1). ΔE ^* _ab = [(ΔL ^* ) ² + (Δa ^* ) ² + (Δb ^* ) ² ] ^1/2 (1) where ΔE ^* _ab : color difference by L ^* a ^* b ^* color system. ΔL ^* ,
Δa ^* , Δb ^* : L ^* a ^* specified in JIS Z 8279
The difference between the CIE1976 lightness L ^{* and} the difference between the color coordinates a ^* and b ^* of two color bodies in the b ^* color system.

ΔE ^* _ab is abbreviated as ΔE. In this report, since the test piece is transparent, a white plate that does not transmit light is attached to the opposite side of the measurement surface. In the case of such a measurement, since the color greatly depends on the film thickness, it is necessary to perform film thickness correction according to Lambert's law when comparing test pieces other than 3 mm. The higher the ΔE value, the more severe the discoloration such as yellowing.

The composition containing the unsaturated polyester and the polymerizable unsaturated monomer of the present invention as the main components has a gloss retention of a cured product having a thickness of 3 mm (a sunshashin wafer based on the ISO standard). The gloss retention after 2000 hours of the weather resistance test with a zometer is 60% or more, preferably 70% or more, and the color difference (ΔE) is 20 or less, preferably 16 or less.
These are: The composition of the present invention can be achieved by appropriately adjusting the components of the unsaturated polyester, the degree of polymerization, and the like, in order to keep the gloss retention and color difference of the cured product within the above ranges.

The conventional unsaturated polyester resin composition does not have a gloss retention of 60% or more and a color difference (ΔE) of 20 or less under the conditions of the above-mentioned weather resistance test. The unsaturated polyester resin composition has the above-mentioned gloss retention and hot-cold shrinkage stress // by adjusting the components constituting the unsaturated polyester, the content thereof, and the composition ratio in the composition as shown in Examples described later. Or, it has a heat-cold shrinkage stress / maximum elastic strength. At the same time, by setting the content of the polymerizable unsaturated monomer to a specific amount, the content of the monomer and the volatility can be suppressed low. It was confirmed that the hull could be formed using the resin adjusted as described above, and the present invention was completed.

A reinforcing material may be added to the composition of the present invention. Examples of such a reinforcing material include glass fiber (chopped strand mat, glass roving cloth, etc.), carbon fiber, and organic fiber (vinylon, polyester,
Phenol, etc.), metal fibers, and the like. 10 to 70% by weight can be used in combination to form FRP, and thus can be used as a synthetic resin layer for a hull skeleton.

The unsaturated polyester resin composition of the present invention is useful as a coating material for synthetic resin hulls, that is, as a paint or gel coat material. When a filler is added, it can be used as a synthetic resin layer for a hull skeleton. These molding methods are not particularly limited, and various methods such as hand lay-up molding, spray-up molding, resin injection molding, preform / matched die molding, and compression molding can be employed.

The resin composition of the present invention may further contain an additive such as a flame retardant, if necessary.

[0060]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited to these Examples. Further, “parts” in the text indicates parts by weight.

Example 1 Production of Unsaturated Polyester Composition 366 parts of neopentyl glycol and ethylene glycol 89 were placed in a 2 L four-necked flask equipped with a thermometer, stirrer, inert gas inlet, and reflux condenser. Part, 2-butyl-2
-88 parts of ethyl-1,3-propanediol, 462 parts of hexahydrophthalic anhydride and 232 parts of fumaric acid were charged, and the temperature was raised to 205 ° C while blowing nitrogen gas.
After reacting for 4 hours, 468 parts of a styrene monomer and 0.13 parts of hydroquinone were added to obtain an unsaturated polyester resin composition having a nonvolatile content of 70% and an acid value of 12.

To 100 parts of the unsaturated polyester resin, Tinuvin 40 of Ciba Specialty Chemicals Co., Ltd. was added.
0, 0.5 parts, Ciba Specialty Chemicals Co., Ltd. Tinuvin 123, 0.4 parts, Asahi Denka Kogyo Co., Ltd.
0.1 part of LA-82 and 50 parts of triethylene glycol dimethacrylate were added to obtain an unsaturated polyester resin composition. This composition has a gloss retention of 95%, a ΔE of 6.5, and a hot / cold shrinkage stress of 15.2 MP according to the following test.
a, Thermal-cold shrinkage stress / maximum elastic strength was 0.97.

Example 2 Production of unsaturated polyester composition In the same manner as in Example 1, 229 parts of neopentyl glycol, 297 parts of 2-methyl-1,3-propanediol, and 308 parts of hexahydrophthalic anhydride were placed in a 2 L flask. And 294 parts of maleic acid were charged, and the temperature was raised to 210 ° C. to carry out an esterification reaction.
85 parts and 0.11 parts of hydroquinone were added,
An unsaturated polyester resin composition having 0% and an acid value of 9 was obtained.
Such a composition has a gloss retention of 78% by the following test,
ΔE was 11.4, hot-cold shrinkage stress was 7.4 MPa, and hot-cold shrinkage stress / maximum elastic strength was 0.31.

Comparative Example 1 Production of Unsaturated Polyester Neopentyl glycol 416 in the same manner as in Example 1.
Parts, propylene glycol (152 parts), hexahydrophthalic anhydride (308 parts), and maleic anhydride (392 parts), and the mixture was heated to 210 ° C. to carry out an esterification reaction.
After the reaction for 7 hours, 749 parts of a styrene monomer and 0.14 parts of hydroquinone were added to obtain an unsaturated polyester resin composition having a nonvolatile content of 60% and an acid value of 5. According to the following test, the composition had a gloss retention (1500 hours) of 40% and a ΔE
Is not measured because the surface whitens and does not accurately represent the color difference even when measured. The hot-cold shrinkage stress was 20.6 MPa, and the hot-cold shrinkage stress / maximum elastic strength was 0.72.

(Test Example) The following tests were conducted using the above unsaturated polyester resin composition. Table 1 summarizes the results.

-Heat-cold shrinkage stress- The hot-cold shrinkage stress at 70 ° C to 20 ° C is measured by the following method. In 100 parts of the resin compositions of the above Examples and Comparative Examples, 0.
Add 5 parts of 6% cobalt naphthenate and 1.0 part of 55% methyl ethyl ketone peroxide, stir, apply the resin on a glass plate so that the thickness of the cured film becomes about 0.3 mm, and allow it to stand at room temperature for 24 hours. Leave to make a cured film. A sample is cut out to a size of 70 mm × 10 mm × about 0.3 mm, and the sample is mounted on Tensilon and heated to at least Tg of the film. The cured film causes a loosening. The sample length is increased and fixed only by the amount of the looseness, and the generated stress is measured while lowering the temperature. The difference between the generated stress at 20 ° C. and 70 ° C. is defined as the hot-cold shrinkage stress of 70 ° C. to 20 ° C.

~ Weather Resistance Test by Sunshine Weatherometer ~ 1) Preparation of Test Plate 55% methyl ethyl ketone peroxide 1.0% was added to the unsaturated polyester resin compositions obtained in Examples and Comparative Examples.
%, 6% cobalt naphthenate 0.1% is added and stirred,
After defoaming, applying a release agent (Furicoat FRP, F-REKOTE), pour the resin onto a sealed glass plate having spacers for adjusting the thickness, then leave it at room temperature for 24 hours, then at 120 ° C for 120 minutes It was further cured to obtain a casting plate having a thickness of about 3 mm.

2) Weather Resistance Test A test piece of 75 mm × 70 mm was cut out from the test plate obtained in the method 1) to prepare a weather resistance test piece. As a weather resistance test method, an accelerated weather resistance test was performed using a sunshine weatherometer (WEL-SUN-HCH-B type manufactured by Suga Test Instruments Co., Ltd.). Test conditions: temperature 63 ± 3 ° C, cycle 1 in 120 minutes
8 minutes rainfall, time 2000 hours

The test pieces were checked every 250 hours, and if the gloss was significantly reduced, the test was stopped.

3) Evaluation of weather resistance Gloss and color difference of the test piece after the test were measured. The measuring equipment is
The gloss meter used was GM26D manufactured by Murakami Color Research Laboratory. The measurement angle was 60 degrees. The gloss retention was determined by gloss retention = mirror gloss after test / mirror gloss before test × 100. The higher the retention ratio, the lower the gloss is. The color difference was measured using a light emitting pipe and a sample table 30 by using Nippon Denshoku Industries Co., Ltd.
Measured in φ and the ΔE value was used for color difference. Higher values indicate more yellowing.

Measurement of Maximum Elastic Strength The maximum elastic strength is measured by the following method. The above embodiment,
To 100 parts of the resin composition of the comparative example, 5 parts of 0.6% cobalt naphthenate and 1.0 part of 55% methyl ethyl ketone peroxide were added and stirred, and the thickness of the cured film was reduced to about 0.3 mm on a glass plate. A resin is applied so as to be left at room temperature for 24 hours and further cured at 60 ° C. for 30 minutes to produce a cured film. 70mm x 10mm x about 0.3m
A sample is cut out to a length of m, and the sample is mounted on Tensilon and measured at a room temperature at a test speed of 5 mm / min. In the initial stage of the strain-stress curve, the strength is determined from the maximum stress in the region according to the linear equation, which is defined as the maximum elastic strength, and the ratio of the above-mentioned hot-cold shrinkage stress / maximum elastic strength is determined.

[0072]

[Table 1]

Further, in order to confirm the weather resistance of the hull, a hull was constructed by the following method. One embodiment of the synthetic resin hull according to the present invention will be described in detail with reference to FIG. 1, but the present invention is not limited to this method alone. FIG. 1 is a sectional view of a synthetic resin hull according to the present invention at the time of manufacture, and FIG. 2 is an enlarged sectional view of a portion A in FIG.

In these figures, reference numeral 1 denotes a synthetic resin hull according to this embodiment, and reference numeral 2 denotes a mold for forming the hull 1. The hull 1 is formed by spraying a synthetic resin on the wall surface of the concave portion 2a of the mold 2 with a spray gun (not shown) so that a plurality of layers are formed as in the conventional case.

As shown in FIG. 2, the synthetic resin layer is composed of a gel coat layer 3 forming a surface layer of the hull 1 and a synthetic resin layer 4 for a skeleton formed inside the gel coat layer 3. In this embodiment, the skeleton synthetic resin layer 4 is formed by spraying a mixture of an unsaturated polyester resin and glass fiber on the inner surface of the gel coat layer with a spray gun.

The gel coat layer 3 is formed by kneading an unsaturated polyester resin with a coloring pigment, finely divided silica, and, if necessary, kneaded with a styrene resin or clay.

The composition of the material constituting the gel coat layer 3 is as follows:
White pigment 5 per 100 parts of unsaturated polyester resin
And 2 parts of finely divided silica. In Table 2 below, an unsaturated polyester resin having excellent weather resistance, a synthetic resin hull 1 in which the gel coat layer of this embodiment was formed and cured in Examples 1 and 2, and a hull was formed with a cured product of the unsaturated polyester resin.
And 2. A hull gel coat layer was formed with the conventional unsaturated polyester resin of Comparative Example 1. A 7 cm × 5 cm test piece was cut out from the hull comparative example 1 and the weathering was promoted by a sunshine weatherometer in the same manner as in the above test example. The test was performed on the gelcoat surface. Table 2 shows the gloss retention and ΔE after a test time of 2000 hours.

[0078]

[Table 2]

[0079]

The resin composition of the present invention is a synthetic resin hull formed by using an unsaturated polyester resin which is excellent in gloss retention and color difference of a cured product, and is excellent in weather resistance including gloss retention and discoloration. Can be provided.

[0080]

[Brief description of the drawings]

FIG. 1 is a cross-sectional view of a synthetic resin hull formed according to the present invention during manufacture.

FIG. 2 is an enlarged cross-sectional view of FIG.

[Explanation of symbols]

1: Hull made of synthetic resin 2: Mold for hull 3: Gel coat layer 4: Synthetic resin layer for skeleton

Claims (10)

[Claims] 1. A cured product comprising (A) an unsaturated polyester and (B) a polymerizable unsaturated monomer and having a gloss retention (a weather resistance measured by a sunshine weatherometer based on ISO standards). A hull made of a synthetic resin, comprising an unsaturated polyester resin composition having a gloss retention (after 2000 hours of the property test) of 60% or more. 2. The synthetic resin hull according to claim 1, wherein the cured product has a hot-cold shrinkage stress at 70 ° C. to 20 ° C. of 17 MPa or less. 3. The synthetic resin hull according to claim 2, wherein the cured product has a heat / cold shrinkage stress / maximum elastic strength of 1 or less. 4. The cured product has a color difference (color difference ΔE of a 3 mm-thick test piece after 2000 hours of a weathering test by a Sunshine Weatherometer based on ISO standards) of 20 or less. Claim 1 or 2 or 3
A hull made of a synthetic resin according to the above. 5. A composition comprising (A) an unsaturated polyester and (B) a polymerizable unsaturated monomer, wherein (A)
The weight ratio between the unsaturated polyester and the polymerizable unsaturated monomer (B) is (A) / (B) = 70/30 to 95/5, wherein the weight ratio is from 70/30 to 95/5. A hull made of synthetic resin as described in Crab. 6. The method according to claim 1, wherein (B) the polymerizable unsaturated monomer is mainly composed of a styrene monomer and an acrylic monomer. A hull made of a synthetic resin according to the above. 7. The unsaturated polyester having a weight ratio of (A) unsaturated polyester and (B) a polymerizable unsaturated monomer having a styrene monomer and an acrylic monomer as main components, which is 5 to 95, respectively. The synthetic resin hull according to claim 6, wherein the styrene monomer is 1 to 30% and the acrylic monomer is 4 to 65%. 8. The synthetic resin hull according to claim 1, further comprising an ultraviolet absorber and / or an ultraviolet stabilizer. 9. A synthetic resin hull comprising a colored surface layer comprising the resin composition according to claim 1 and a synthetic resin base layer. 10. The synthetic resin hull according to claim 9, wherein the synthetic resin base layer comprises the resin composition according to any one of claims 1 to 8 containing a reinforcing material.