JPH0780952A - Molding of fiber reinforced plastic and molded product - Google Patents

Abstract

PURPOSE:To simplify an impregnation and defoaming process, to reduce labor and to increase a molding cycle by spraying a composition consisting of a hollow filler and a specific resin containing a thixotropy imparting agent and a fiber reinforcing material on the single surface of a molded product composed of a specific resin to cure the same. CONSTITUTION:A compsn. consisting of a spherical hollow filler and an unsaturated polyester resin or a vinyl ester resin containing a thixotropy imparting agent and a fiber reinforcing material are sprayed on the single surface of a molded article made of the unsaturated polyester resin or the vinyl ester resin to be cured. Herein, the viscosity of the unsaturated polyester resin and/or the vinyl ester resin containing the spherical hollow filler and the thixotropy imparting agent is 10-50 poise and the thixotropy thereof is pref. 4-9. Further, the spherical hollow filler pref. has a diameter of 10-300mum and specific gravity of 0.02-0.8. The content of the filler is pref. 5.0-60% by volume of the unsaturated polyester resin and/or the vinyl ester resin.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a molded product made of unsaturated polyester resin or vinyl ester resin, for example, FRP obtained by molding by hand lay-up, spray-up, casting, resin injection, press molding, etc.
FR made by spraying and curing a specific resin composition on one side of a molded product such as a bathtub made of FRP, a bathtub with a floor-standing washing room, a waterproof pan made of FRP, an artificial marble bathtub, a septic tank, and a boat.
The present invention relates to a method for molding a fiber-reinforced plastic having a P layer and a molded product thereof.

[0002]

2. Description of the Related Art Conventionally, an FRP bathtub and a FRP stationary washroom obtained by molding methods such as hand lay-up, spray-up, casting, resin injection and press using unsaturated polyester resin or vinyl ester resin as matrix resin. The attached bathtub, FRP waterproof pan, artificial marble bathtub, septic tank, boat, etc. are composed of the surface layer, the intermediate layer, the back layer, and a combination thereof, and are made of plywood, metal to obtain rigidity that can withstand transportation, construction, and use. It is generally commercialized by partially reinforcing or thickening it with a frame made of a product. The joining with the reinforcing material and the thickness increasing process are partially performed again by ordinary hand lay-up and spray-up molding. Further, the joint portion with the reinforcing material is also subdivided, and particularly the impregnation and defoaming step of the joint portion requires elaborate manual finishing work. Such a reinforcement process consumes most of the entire molding time and is the rate-determining factor for the mold and molding cycle.

The hand lay-up, reinforcement by spray-up molding, and thickening process referred to here are the former to a chopped strand mat having a fiber length of about 2 inches and the latter to a chopped strand of about 1 inch. This is a generally known FRP molding method in which a thermosetting resin is impregnated using a foam roller and cured.

[0004]

DISCLOSURE OF THE INVENTION An object of the present invention is to provide an impregnating and defoaming process which spends most of the entire molding time in the conventional hand lay-up, reinforcement and thickening processes performed by spray-up molding. This is a molding method that simplifies and reduces manpower involved, and enables a molding cycle to be increased.

As a result of intensive studies, the present inventors have completed the present invention by overcoming the above problems with a specific resin composition.

[0006]

That is, the present invention is an unsaturated polyester resin containing a spherical hollow filler and a thixotropic agent on one surface of a molded product of an unsaturated polyester resin or a vinyl ester resin, and / or The present invention relates to a molding method and a molded article of a fiber reinforced plastic, which comprises spraying a composition comprising a vinyl ester resin and a fiber reinforced material to cure the composition. The viscosity of the resin composition is preferably 10 to 50 poise, the thixotropic property of the resin composition is preferably 4 to 9, the hollow filler is preferably 10 to 300 microns in diameter, and the specific gravity is 0.02.
To 0.8, preferably the hollow filler content is 5 to 60% by volume in the resin composition, and the resin molded product thus obtained is provided.

According to the molding method of the present invention, the fiber reinforcement and the unsaturated polyester resin liquid and / or vinyl ester resin liquid containing the spherical hollow filler and the thixotropic agent are sprayed on one surface of the molded product. The FRP layer thus formed can complete the impregnation and defoaming process with almost no human labor, and has rigidity that can withstand transportation, construction, and use,
Reinforcement and thickening can be added, enabling labor-saving and quick production of fiber-reinforced plastic products.

(Constitution) The unsaturated polyester resin or vinyl ester resin molding of the present invention has a thickness of 0.0
It is a molded product of about 1 to 20 mm, and its shape may be any. This molded product is a surface layer formed by an existing generally known molding method such as hand layup, spray up, casting, resin injection, press molding,
It means a fiber-reinforced plastics or non-fiber-reinforced plastics semi-finished product composed of an intermediate layer, a back layer, and a combination thereof.

The resin used in the molded article made of the unsaturated polyester resin or vinyl ester resin of the present invention is not particularly limited in composition, and a generally known resin can be used. Preferably, the α, β-unsaturated monomer is from 60 to
The α, β-unsaturated monomer, which is contained at 30% by weight, includes styrene, α-methylstyrene, methylmethacrylate, ethylmethacrylate, β-hydroxyethylmethacrylate and the like. This molding is
It contains a filler and / or a fiber reinforcement.

The unsaturated polyester resin used in the spraying of the present invention is not particularly limited, and is an unsaturated dibasic acid, an anhydride thereof, a saturated dibasic acid or an anhydride thereof, a glycol, or a carbon number. What was obtained by dehydration condensation polymerization of 2-3 alkylene oxides was dissolved in α, β-unsaturated monomers such as styrene, α-methylstyrene, methyl methacrylate, ethyl methacrylate, β-hydroxyethyl methacrylate. It is a thing. This α, β-unsaturated monomer may be further added in order to adjust the viscosity of the composition to 10 to 50 poise which is preferable for spray-up.

The vinyl ester resin used for spraying of the present invention is prepared by reacting methacrylic acid, acrylic acid or the like with the terminal of an existing bisphenol-based or novolac-based epoxy resin to obtain styrene, α, as in the unsaturated polyester resin. -Dissolved in α, β-unsaturated monomers such as methylstyrene, methylmethacrylate, ethylmethacrylate and β-hydroxyethylmethacrylate. This α, β-unsaturated monomer may be further added in order to adjust the viscosity of the composition to 10 to 50 poise which is preferable for spray-up.

The unsaturated polyester resin and vinyl ester resin used in the spraying of the present invention preferably contain 60 to 30% by weight of an α, β-unsaturated monomer. The β-unsaturated monomer may be the same as above.

The spherical hollow filler of the present invention is not particularly limited, and generally known ones can be used, and the material thereof is an inorganic material such as glass, silica, ceramics, or vinylidene chloride. There is no particular limitation as to organic substances such as acrylics, acrylic-acrylonitrile copolymers and the like, and further those with or without surface treatment. The particle size may be such that it can pass through the nozzle of the sprayer, and the particle size is preferably 10 to 300.
Micron, more preferably 15 to 200 microns, and its true specific gravity is about 0.02 to 0.8. The value varies greatly depending on whether it is inorganic or organic. Further, the pressure resistance is preferably high in order to prevent damage during mixing and molding. Its strength is preferably 5~1000kg / cm ^2, particularly preferably 100 kg / cm ² or more.

As commercially available products, for example, Scotch light glass bubble (Sumitomo 3M), MIRALITE,
MICRLITE, Dualite (PIERCE & S
TEVENS), Glass Microballo
on (manufactured by EMERSPON & CUMING), Q-C
EL, Microcel (manufactured by Asahi Glass Co., Ltd.), Expancel, Microcel (manufactured by Nippon Philite Co., Ltd.), MFL
-80CA (manufactured by Matsumoto Yushi Co., Ltd.) or the like can be used.

The amount of the hollow filler added is preferably 5.0 to 60% by volume (in the resin composition), and more preferably 7.0 to 50% by volume (in the resin composition).

The thixotropic agent of the present invention is not particularly limited in its shape such as a star shape, a needle shape, a whisker shape, or an adjoining piece shape, and is a liquid unsaturated polyester or vinyl ester resin composition. Any property or shape that gives denaturation may be used. Specific examples thereof include silica powder, talc powder, mica powder, glass flakes, metal whiskers, ceramic whiskers, calcium sulfate whiskers, asbestos, smectite and the like. If necessary, the above two or more kinds may be used in combination.

As commercially available products, Leoroseal QS series (manufactured by Tokuyama Soda Co., Ltd.), Aerosil series (manufactured by Nippon Aerosil Co., Ltd.), BENATHIX series (manufactured by Wilber Ellis Co., Ltd.), FRANNKLIN FIBER (U
SG), talc SW, SS, SWE, (Nippon Talc), talcan powder PK, Rotaruku T (Hayashi Kasei), Arbolex YS (Shikoku Kasei).

The size and particle size are not particularly limited as long as they can pass through a spray-up machine, and preferably 1 to 20 parts by weight (based on the resin composition). Yes, it is determined by the thixotropic ability of the thixotropic agent.

The curing catalyst is not particularly limited, and generally known ones can be used, for example, methyl ethyl ketone peroxide, cyclohexane peroxide, acetylacetone peroxide, acetoacetic acid ester peroxide, benzoyl peroxide and the like. Examples thereof include peroxide catalysts, and two or more of these may be used in combination. The amount added is preferably 0.5 to 5 parts by weight per 100 parts of the composition.

The curing accelerator is not particularly limited and includes metal salts and chelates of organic acids, such as cobalt naphthenate, cobalt octylate, acetylacetone cobalt or the like, or amines such as
Examples thereof include dimethylaniline and diethylaniline, and two or more of these may be used in combination. The amount added is preferably 0.01 to 5 parts by weight per 100 parts by weight of the composition.

If necessary, a defoaming agent, a modifier and the like may be added.

The fiber reinforcing material of the present invention is, for example, glass fiber, aramid fiber, vinylon fiber, polyester fiber, nylon fiber, carbon fiber, metal fiber or the like or a combination thereof. Glass fiber and carbon fiber are preferable. Moreover, the form of the fiber is preferably a string-like or roving-like form. It is also possible to cut a string-like or roving-like product into a length of 3 to 25 mm in advance and use it as chopped strands. The preferred fiber length is 3 to 50 mm, particularly preferably 3 to 25 mm. The fiber reinforcement is usually sprayed with the composition and applied to the substrate when spray-up molding. However, the spray nozzles are separate ports.

The weight ratio of the fiber reinforcement is preferably 5 to 30% by weight, more preferably 5 to 30% by weight in the composition of unsaturated polyester resin and vinyl ester resin.
25% by weight, particularly preferably 8 to 20% by weight.

If desired, the unsaturated polyester resin composition and / or vinyl ester resin composition of the present invention may be mixed with a pigment, another filler, a shrinkage reducing agent, a defoaming agent and the like. . As the pigment and the shrinkage reducing agent, those for general commercially available unsaturated polyester resin may be used.

Other fillers are used for the purpose of increasing the amount of raw materials, and examples thereof include powders of calcium carbonate, silica, glass, alumina, clay, aluminum hydroxide, barium sulfate, calcium sulfate, silica stone, etc., and their particles. The diameter may be any size as long as it can pass through the spray-up machine. Moreover, you may use together 2 or more types of these.

The composition of unsaturated polyester resin or vinyl ester resin containing the spherical hollow filler and the thixotropic agent used in the present invention preferably has a viscosity of 10 to 5.
0 poise, more preferably 10-30 poise (JI
SK-6901 4, 5), and the thixotropy is preferably 4.0 to 9.0, particularly preferably 4.0 to 7.0 (JI.
SK-6901 4, 5), and the gelation time is preferably 2 to 30 minutes (JIS-K-6901 4, 8).
Is. If the viscosity and thixotropy are out of this range, spray-up molding becomes difficult, which is not preferable.

Molded articles to which the molding method of the present invention is applied include FRP bathtubs made of unsaturated polyester or vinyl ester resin, FRP bathtubs with a floor-standing type washing room,
FRP waterproof pan, artificial marble bath, septic tank, boat,
There are table materials, wall materials, floor materials, kitchen materials, automobile parts, electric parts, statues, etc.

The FRP spray-up molding method of the present invention uses a commercially available spray gun and a chopper to prepare an unsaturated polyester resin liquid and / or a vinyl ester resin liquid containing a spherical hollow filler and a thixotropic agent and A fiber reinforcing material having a size of 3 to 25 mm is sprayed onto one surface of an unsaturated polyester resin or vinyl ester resin molding to cure it.

[0029]

EXAMPLES The present invention will be described in detail below with reference to synthesis examples, examples and comparative examples, but "parts" and "%" are based on weight.

Reference Example-1 (Bathtub FRP with a stationary washing place
Molding of Substrate) (Mold release treatment) After cleaning the mold surface of a 1800 × 1500 mm bathtub type with a stationary washing place, a release agent-free coat FRP was applied and dried at 50 ° C. for 30 minutes to perform mold release treatment (1 -
).

(Coating with gel coat) 100 parts of unsaturated polyester resin GC-560 for gel coat (manufactured by Dainippon Ink and Chemicals, Inc.) and pigment POLYTON J-
107A (manufactured by Dainippon Ink and Chemicals, Inc.) 10 parts,
6% cobalt naphthenate 0.4 parts and permek N (manufactured by NOF CORPORATION) 1.0 parts were mixed, and the mold had a thickness of about 0.4.
After being applied to the mm, after-curing was performed at 50 ° C. for 30 minutes. (1-)

(Spray-up molding of intermediate layer) 100 parts of unsaturated polyester resin Polylite LP-924-N (manufactured by Dainippon Ink and Chemicals, Inc.) per 1.0 parts of Permek N N, 1-inch long glass roving ER231
50 parts of 0SP-10 (manufactured by Asahi Fiber Glass Co., Ltd.) was applied by spray-up to the above-mentioned mold coated with gel coat, and impregnated with a roll and after-cured at 60 ° C. for 30 minutes to form an FRP layer of about 1 mm. , An intermediate layer was obtained. (1-)

(Molding of back layer) 100 parts of unsaturated polyester resin polylite LP-821-N (manufactured by Dainippon Ink and Chemicals, Inc.) per 100 parts of Permek N1.0
Part, 1 inch long glass roving ER2310SP-1
Fifty parts of 0 (manufactured by Asahi Fiber Glass Co., Ltd.) was sprayed up onto the above-mentioned mold (1-) coated with a gel coat, and an FRP layer of about 2 mm was formed by roll impregnation to obtain a back layer. (1-)

(Adhesion of Reinforcing Material) A 6 mm plywood and a metal frame for reinforcement are adhered to a predetermined portion on the above-mentioned intermediate layer (1-) with a stationary washing basin, and 60 together with the back layer.
After-curing was performed at 30 ° C. for 30 minutes. (1-)

Example 1 (molding of FRP layer) 100 parts of unsaturated polyester resin Polylite 8010 (manufactured by Dainippon Ink and Chemicals, Inc.) was used as a thixotropic agent, and silica powder Rheorosil QS-20 (Tokuyama Soda ( Co., Ltd.) 2.5 parts, 6% cobalt naphthenate 0.4
Part, dimethylaniline 0.1 part, styrene monomer 50
The parts were mixed to obtain an unsaturated polyester resin A-1.

Next, unsaturated polyester resin A-110
Hollow filler DUALITE M6017AE for 0 parts
(Pierce & Stephen) 16% by volume, and talc SW as a thixotropic agent (Nippon Talc Co., Ltd.)
10 parts, a filler and 70 parts of calcium carbonate NS-100 (manufactured by Nitto Koka Co., Ltd.) were added and stirred to obtain a resin compound C-1.

The resulting resin compound C-1 had a viscosity of 1
8.0 poise, thixotropic 5.6, gelation time 4 minutes (JIS K 6901
4,8). Permek N 1.0 part for 100 parts of C-1, 16 mm long glass roving GR-31
25 parts (manufactured by Nippon Sheet Glass Co., Ltd.) was sprayed up onto a bathtub molding (1-) with a stationary washing place to which a reinforcing material was adhered, and after the roll impregnation step was not performed, it was post-cured at 60 ° C. for 30 minutes to a thickness of about 2 mm. Overlayed F
An RP layer was obtained. (1-A-)

After demolding, a bathtub with a stationary washing place in which the gel coat layer, the intermediate layer, the back layer and the FRP layer are integrated (1
-A-).

The obtained bathtub with a stationary washing room (1-A-
) Satisfies the performance of JIS A 5712 (bathtub with glass fiber reinforced polyester washroom),
It was effective in shortening the work time and the number of workers. The evaluation results are shown in Table-1.

Comparative Example-1 (Molding of FRP layer) The FRP layer was molded in the same manner up to the adhesion of the reinforcing material of Reference Example-1. Unsaturated polyester resin polylite LP-
821-N (manufactured by Dainippon Ink and Chemicals, Inc.) 100
For each part, Permek N 1.0 part, 1 inch long glass roving ER2310SP-10 (manufactured by Asahi Fiber Glass Co., Ltd.) 50 parts were sprayed up on the above-mentioned molded article (1-) coated with a gel coat, and after impregnation with a roll, 60 ° C
After curing for 30 minutes, a FRP layer with an overlay of about 2 mm was obtained. (1-B-)

After demolding, a bathtub with a stationary washing place in which the gel coat layer, the intermediate layer, the back layer and the FRP layer are integrated (1
-B-)

The obtained bathtub with a stationary washing room (1-B-
) Satisfied the performance of JIS A 5712, but required a long working time and required a large number of personnel.
The evaluation results are shown in Table 1.

[0043]

[Table 1]

Reference Example-2 (Molding of Artificial Marble Bathtub) An artificial marble bathtub was prepared using a generally known casting and room temperature curing system by using a vinyl ester resin and a stone tone filler. (2-)

Example-2 (Molding of FRP layer) Unsaturated polyester resin "Polylite FS-150"
90 parts (manufactured by Dainippon Ink and Chemicals, Inc.) was mixed with 0.1 part of dimethylaniline and 10 parts of styrene monomer to obtain unsaturated polyester resin A-2.

Hollow filler "D" was added to 100 parts of A-2.
UALITE M6017AE (PIERCE & STE
13% by volume, 15 parts of talc SW (manufactured by Nippon Talc Co., Ltd.) as a thixotropic agent, and 60 parts of filler "calcium carbonate NS-100 (manufactured by Nitto Koka Co., Ltd.)". Then, the mixture was stirred to obtain a resin compound C-2.

The obtained resin compound C-2 had a viscosity of 17.0 poise, a thixotropic property of 4.5, and a gelation time of 3 minutes (JIS K
6901 4,8).

Permek N for 100 parts of C-2
1.0 part, 16mm long glass roving "ER231
25 parts of "0SP-10 (manufactured by Asahi Fiber Glass Co., Ltd.)" was sprayed up into an artificial marble bath (2-), and the roll impregnation step was not performed, after-curing was performed at 60 ° C for 30 minutes, and the overlayed FRP was formed with a thickness of about 1 mm. An artificial marble bath having layers was obtained. (2-A-)

The obtained artificial marble bathtub (2-A-) is
The performance was satisfactory, and it was effective in shortening the work time and reducing the number of personnel. The evaluation results are shown in Table 2.

Example-3 (molding of FRP layer) The procedure up to the molding of the artificial marble bath of Reference Example-2 was performed in the same manner,
The FRP layer was molded.

Unsaturated polyester resin "Polylite 80"
10 (manufactured by Dainippon Ink and Chemicals, Incorporated) "100 parts" against thixotropic agent "silica powder, Reorosil QS-"
20 (manufactured by Tokuyama Soda Co., Ltd.) ", 2.5 parts, 6% cobalt naphthenate 0.4 parts, dimethylaniline 0.1 part, and styrene monomer 45 parts are mixed to obtain an unsaturated polyester resin A-3. It was

Next, unsaturated polyester resin A-110
Hollow filler "DUALITE M6017A" for 0 parts
E (manufactured by PIERCE & STEPN) "7.5% by volume
Were mixed to obtain a resin compound C-3.

The obtained resin compound C-3 had a viscosity of 28.0 poise, thixotropic property of 5.6 and gelation time of 3 minutes (JIS K
6901 4,8).

Permek N for 100 parts of C-3
1.0 part, 16 mm long glass roving ER2310S
Twenty-five parts of P-10 (manufactured by Asahi Fiber Glass Co., Ltd.) was applied to the artificial marble bath (2-) without performing the roll impregnation step,
After curing at 60 ° C. for 30 minutes, an artificial marble bath having an FRP layer overlaid with a thickness of about 1 mm was obtained. (3-A-)

The obtained artificial marble bathtub (3-A-) is
The performance was satisfied, and it was effective in shortening the work time and reducing the number of personnel. The evaluation results are shown in Table 2.

Comparative Example-2 (Molding of FRP layer) FRP was similarly processed until the artificial marble bath of Example-2 was molded.
The layers were molded. To 100 parts of unsaturated polyester resin "Polylite LP-821-N (manufactured by Dainippon Ink and Chemicals, Inc.)", Permeck N 1.0 part, 1 part
50 parts of inch-long glass roving ER2310SP-10 (manufactured by Asahi Fiber Glass Co., Ltd.) was sprayed up into the artificial marble bath (2-), and after the roll impregnation step, 60
After curing at 30 ° C. for 30 minutes, an artificial marble bath having an FRP layer overlaid with a thickness of about 1 mm was obtained. (2-B-)

The artificial marble bathtub (2-B-) obtained was
Although it satisfied the performance, it required a long working time and required a large number of workers. The evaluation results are shown in Table 2.

[0058]

[Table 2]

[0059]

The advantage of the present invention is that when forming an FRP layer for reinforcing or thickening a molded article such as plastic, it is possible to omit the impregnation defoaming step which conventionally had to rely on manual work. However, the process after spraying is almost unnecessary.

That is, the molding process of the FRP layer can be greatly simplified, the molding time can be shortened, and the number of workers can be reduced. Also, since the roll impregnation step is unnecessary,
It has the merit that the gelling time of the resin can be set extremely short and the process can be immediately moved to the next step.

Further, the FRP layer molding according to the present invention can be automated by a robot and the like, and it is possible to eliminate manpower from a working environment in which a monomer odor drifts, and to obtain an excellent effect on hygiene.

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[Procedure amendment]

[Submission date] October 26, 1994

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be amended] Detailed explanation of the invention

[Correction method] Change

[Correction content]

Detailed Description of the Invention

[0001]

The present invention relates to a molded product made of unsaturated polyester resin or vinyl ester resin, for example, FRP obtained by molding by hand lay-up, spray-up, casting, resin injection, press molding, etc.
FR made by spraying and curing a specific resin composition on one side of a molded product such as a bathtub made of FRP, a bathtub with a floor-standing washing room, a waterproof pan made of FRP, an artificial marble bathtub, a septic tank, and a boat.
The present invention relates to a method for molding a fiber-reinforced plastic having a P layer and a molded product thereof.

[0002]

2. Description of the Related Art Conventionally, an FRP bathtub and a FRP stationary washroom obtained by molding methods such as hand lay-up, spray-up, casting, resin injection and press using unsaturated polyester resin or vinyl ester resin as matrix resin. The attached bathtub, FRP waterproof pan, artificial marble bathtub, septic tank, boat, etc. are composed of the surface layer, the intermediate layer, the back layer, and a combination thereof, and are made of plywood, metal to obtain rigidity that can withstand transportation, construction, and use. It is generally commercialized by partially reinforcing or thickening it with a frame made of a product. The joining with the reinforcing material and the thickness increasing process are partially performed again by ordinary hand lay-up and spray-up molding. Further, the joint portion with the reinforcing material is also subdivided, and particularly the impregnation and defoaming step of the joint portion requires elaborate manual finishing work. Such a reinforcement process consumes most of the entire molding time and is the rate-determining factor for the mold and molding cycle.

The hand lay-up, reinforcement by spray-up molding, and thickening process referred to here are the former to a chopped strand mat having a fiber length of about 2 inches and the latter to a chopped strand of about 1 inch. This is a generally known FRP molding method in which a thermosetting resin is impregnated using a foam roller and cured.

[0004]

DISCLOSURE OF THE INVENTION An object of the present invention is to provide an impregnating and defoaming process which spends most of the entire molding time in the conventional hand lay-up, reinforcement and thickening processes performed by spray-up molding. This is a molding method that simplifies and reduces manpower involved, and enables a molding cycle to be increased.

As a result of intensive studies, the present inventors have completed the present invention by overcoming the above problems with a specific resin composition.

[0006]

That is, the present invention is an unsaturated polyester resin containing a spherical hollow filler and a thixotropic agent on one surface of a molded product of an unsaturated polyester resin or a vinyl ester resin, and / or The present invention relates to a molding method and a molded article of a fiber reinforced plastic, which comprises spraying a composition comprising a vinyl ester resin and a fiber reinforced material to cure the composition. The viscosity of the resin composition is preferably 10 to 50 poise, the thixotropic property of the resin composition is preferably 4 to 9, the hollow filler is preferably 10 to 300 microns in diameter, and the specific gravity is 0.02.
To 0.8, preferably the hollow filler content is 5 to 60% by volume in the resin composition, and the resin molded product thus obtained is provided.

According to the molding method of the present invention, the fiber reinforcement and the unsaturated polyester resin liquid and / or vinyl ester resin liquid containing the spherical hollow filler and the thixotropic agent are sprayed on one surface of the molded product. The FRP layer thus formed can complete the impregnation and defoaming process with almost no human labor, and has rigidity that can withstand transportation, construction, and use,
Reinforcement and thickening can be added, enabling labor-saving and quick production of fiber-reinforced plastic products.

(Constitution) The unsaturated polyester resin or vinyl ester resin molding of the present invention has a thickness of 0.0
It is a molded product of about 1 to 20 mm, and its shape may be any. This molded product is a surface layer formed by an existing generally known molding method such as hand layup, spray up, casting, resin injection, press molding,
It means a fiber reinforced plastics or non-fiber reinforced plastics semi-finished product composed of an intermediate layer, a back layer and a combination thereof.

The resin used in the molded article made of the unsaturated polyester resin or vinyl ester resin of the present invention is not particularly limited in composition, and a generally known resin can be used. Preferably, the α, β-unsaturated monomer is from 60 to
The α, β-unsaturated monomer, which is contained at 30% by weight, includes styrene, α-methylstyrene, methylmethacrylate, ethylmethacrylate, β-hydroxyethylmethacrylate and the like. This molding is
It contains a filler and / or a fiber reinforcement.

The unsaturated polyester resin used in the spraying of the present invention is not particularly limited, and is an unsaturated dibasic acid, an anhydride thereof, a saturated dibasic acid or an anhydride thereof, a glycol, or a carbon number. What was obtained by dehydration condensation polymerization of 2-3 alkylene oxides was dissolved in α, β-unsaturated monomers such as styrene, α-methylstyrene, methyl methacrylate, ethyl methacrylate, β-hydroxyethyl methacrylate. It is a thing. This α, β-unsaturated monomer may be further added in order to adjust the viscosity of the composition to 10 to 50 poise which is preferable for spray-up.

The vinyl ester resin used for spraying of the present invention is prepared by reacting methacrylic acid, acrylic acid or the like with the terminal of an existing bisphenol-based or novolac-based epoxy resin to obtain styrene, α, as in the unsaturated polyester resin. -Dissolved in α, β-unsaturated monomers such as methylstyrene, methylmethacrylate, ethylmethacrylate and β-hydroxyethylmethacrylate. This α, β-unsaturated monomer may be further added in order to adjust the viscosity of the composition to 10 to 50 poise which is preferable for spray-up.

The unsaturated polyester resin and vinyl ester resin used in the spraying of the present invention preferably contain 60 to 30% by weight of an α, β-unsaturated monomer. The β-unsaturated monomer may be the same as above.

The spherical hollow filler of the present invention is not particularly limited, and generally known ones can be used, and the material thereof is an inorganic material such as glass, silica, ceramics, or vinylidene chloride. There is no particular limitation as to organic substances such as acrylics, acrylic-acrylonitrile copolymers and the like, and further those with or without surface treatment. The particle size may be such that it can pass through the nozzle of the sprayer, and the particle size is preferably 10 to 300.
Micron, more preferably 15 to 200 microns, and its true specific gravity is about 0.02 to 0.8. The value varies greatly depending on whether it is inorganic or organic. Further, the pressure resistance is preferably high in order to prevent damage during mixing and molding. Its strength is preferably 5~1000kg / cm ^2, particularly preferably 100 kg / cm ² or more.

As commercially available products, for example, Scotch light glass bubble (Sumitomo 3M), MIRALITE,
MICRLITE, Dualite (PIERCE & S
TEVENS), Glass Microballo
on (manufactured by EMERSPON & CUMING), Q-C
EL, Microcel (manufactured by Asahi Glass Co., Ltd.), Expancel, Microcel (manufactured by Nippon Philite Co., Ltd.), MFL
-80CA (manufactured by Matsumoto Yushi Co., Ltd.) or the like can be used.

The amount of the hollow filler added is preferably 5.0 to 60% by volume (in the resin composition), and more preferably 7.0 to 50% by volume (in the resin composition).

The thixotropic agent of the present invention is not particularly limited in its shape such as a star shape, a needle shape, a whisker shape, or an adjoining piece shape, and is a liquid unsaturated polyester or vinyl ester resin composition. Any property or shape that gives denaturation may be used. Specific examples include silica powder, talc powder, glass flakes, metal whiskers, ceramic whiskers, calcium sulfate whiskers, asbestos, smectite, and the like. If necessary, the above two or more kinds may be used in combination.

As commercially available products, Leoroseal QS series (manufactured by Tokuyama Soda Co., Ltd.), Aerosil series (manufactured by Nippon Aerosil Co., Ltd.), BENATHIX series (manufactured by Wilber Ellis Co., Ltd.), FRANNKLIN FIBER (U
SG), talc SW, SS, SWE, (Nippon Talc), talcan powder PK, Rotaruku T (Hayashi Kasei), Arbolex YS (Shikoku Kasei).

The size and particle size are not particularly limited as long as they can pass through a spray-up machine, and preferably 1 to 20 parts by weight (based on the resin composition). Yes, it is determined by the thixotropic ability of the thixotropic agent.

The curing catalyst is not particularly limited, and generally known ones can be used, for example, methyl ethyl ketone peroxide, cyclohexane peroxide, acetylacetone peroxide, acetoacetic acid ester peroxide, benzoyl peroxide and the like. Examples thereof include peroxide catalysts, and two or more of these may be used in combination. The amount added is preferably 0.5 to 5 parts by weight per 100 parts of the composition.

The curing accelerator is not particularly limited and includes metal salts and chelates of organic acids, such as cobalt naphthenate, cobalt octylate, acetylacetone cobalt or the like, or amines such as
Examples thereof include dimethylaniline and diethylaniline, and two or more of these may be used in combination. The amount added is preferably 0.01 to 5 parts by weight per 100 parts by weight of the composition.

If necessary, a defoaming agent, a modifier and the like may be added.

The fiber reinforcing material of the present invention is, for example, glass fiber, aramid fiber, vinylon fiber, polyester fiber, nylon fiber, carbon fiber, metal fiber or the like or a combination thereof. Glass fiber and carbon fiber are preferable. Moreover, the form of the fiber is preferably a string-like or roving-like form. It is also possible to cut a string-like or roving-like product into a length of 3 to 25 mm in advance and use it as chopped strands. The preferred fiber length is 3 to 50 mm, particularly preferably 3 to 25 mm. The fiber reinforcement is usually sprayed with the composition and applied to the substrate when spray-up molding. However, the spray nozzles are separate ports.

The weight ratio of the fiber reinforcement is preferably 5 to 30% by weight, more preferably 5 to 30% by weight in the composition of unsaturated polyester resin and vinyl ester resin.
25% by weight, particularly preferably 8 to 20% by weight.

If desired, the unsaturated polyester resin composition and / or vinyl ester resin composition of the present invention may be mixed with a pigment, another filler, a shrinkage reducing agent, a defoaming agent and the like. . As the pigment and the shrinkage reducing agent, those for general commercially available unsaturated polyester resin may be used.

Other fillers are used for the purpose of increasing the amount of raw materials, and examples thereof include powders of calcium carbonate, silica, glass, alumina, clay, aluminum hydroxide, barium sulfate, calcium sulfate, silica stone, etc., and their particles. The diameter may be any size as long as it can pass through the spray up machine. Moreover, you may use together 2 or more types of these.

The composition of unsaturated polyester resin or vinyl ester resin containing the spherical hollow filler and the thixotropic agent used in the present invention preferably has a viscosity of 10 to 5.
0 poise, more preferably 10-30 poise (JI
SK-6901 4, 5), and the thixotropy is preferably 4.0 to 9.0, particularly preferably 4.0 to 7.0 (JI.
SK-6901 4, 5), and the gelation time is preferably 2 to 30 minutes (JIS-K-6901 4, 8).
Is. If the viscosity and thixotropy are out of this range, spray-up molding becomes difficult, which is not preferable.

Molded articles to which the molding method of the present invention is applied include FRP bathtubs made of unsaturated polyester or vinyl ester resin, FRP bathtubs with a floor-standing type washing room,
FRP waterproof pan, artificial marble bath, septic tank, boat,
There are table materials, wall materials, floor materials, kitchen materials, automobile parts, electric parts, statues, etc.

The FRP spray-up molding method of the present invention uses a commercially available spray gun and a chopper to prepare an unsaturated polyester resin liquid and / or a vinyl ester resin liquid containing a spherical hollow filler and a thixotropic agent and A fiber reinforcing material having a size of 3 to 25 mm is sprayed onto one surface of an unsaturated polyester resin or vinyl ester resin molding to cure it.

[0029]

EXAMPLES The present invention will be described in detail below with reference to synthesis examples, examples and comparative examples, but "parts" and "%" are based on weight.

Reference Example-1 (Bathtub FRP with a stationary washing place
Molding of Substrate) (Mold release treatment) After cleaning the mold surface of a 1800 × 1500 mm bathtub type with a stationary washing place, a mold release agent free coat FRP was applied and dried at 50 ° C. for 30 minutes to perform mold release treatment (1 -
).

(Coating with gel coat) 100 parts of unsaturated polyester resin GC-560 for gel coat (manufactured by Dainippon Ink and Chemicals, Inc.) and pigment POLYTON J-
107A (manufactured by Dainippon Ink and Chemicals, Inc.) 10 parts,
6% cobalt naphthenate 0.4 parts and permek N (manufactured by NOF CORPORATION) 1.0 parts were mixed, and the mold had a thickness of about 0.4.
After being applied to the mm, after-curing was performed at 50 ° C. for 30 minutes. (1-)

(Spray-up molding of intermediate layer) 100 parts of unsaturated polyester resin Polylite LP-924-N (manufactured by Dainippon Ink and Chemicals, Inc.) per 1.0 parts of Permek N N, 1-inch long glass roving ER231
50 parts of 0SP-10 (manufactured by Asahi Fiber Glass Co., Ltd.) was applied by spray-up to the above-mentioned mold coated with gel coat, and impregnated with a roll and after-cured at 60 ° C. for 30 minutes to form an FRP layer of about 1 mm. , An intermediate layer was obtained. (1-)

(Molding of back layer) 100 parts of unsaturated polyester resin polylite LP-821-N (manufactured by Dainippon Ink and Chemicals, Inc.) per 100 parts of Permek N1.0
Part, 1 inch long glass roving ER2310SP-1
Fifty parts of 0 (manufactured by Asahi Fiber Glass Co., Ltd.) was sprayed up onto the above-mentioned mold (1-) coated with a gel coat, and an FRP layer of about 2 mm was formed by roll impregnation to obtain a back layer. (1-)

(Adhesion of Reinforcing Material) A 6 mm plywood and a metal frame for reinforcement are adhered to a predetermined portion on the above-mentioned intermediate layer (1-) with a stationary washing basin, and 60 together with the back layer.
After-curing was performed at 30 ° C. for 30 minutes. (1-)

Example 1 (molding of FRP layer) 100 parts of unsaturated polyester resin Polylite 8010 (manufactured by Dainippon Ink and Chemicals, Inc.) was used as a thixotropic agent, and silica powder Rheorosil QS-20 (Tokuyama Soda ( Co., Ltd.) 2.5 parts, 6% cobalt naphthenate 0.4
Part, dimethylaniline 0.1 part, styrene monomer 50
The parts were mixed to obtain an unsaturated polyester resin A-1.

Next, unsaturated polyester resin A-110
Hollow filler DUALITE M6017AE for 0 parts
(Pierce & Stephen) 16% by volume, and talc SW as a thixotropic agent (Nippon Talc Co., Ltd.)
10 parts, a filler and 70 parts of calcium carbonate NS-100 (manufactured by Nitto Koka Co., Ltd.) were added and stirred to obtain a resin compound C-1.

The resulting resin compound C-1 had a viscosity of 1
8.0 poise, thixotropic 5.6, gelation time 4 minutes (JIS K 6901
4,8). Permek N 1.0 part for 100 parts of C-1, 16 mm long glass roving GR-31
25 parts (manufactured by Nippon Sheet Glass Co., Ltd.) was sprayed up onto a bathtub molding (1) with a stationary washing place to which a reinforcing material was adhered, and after roll-impregnation step was not performed, after-curing was performed for 30 minutes at 60 ° C. Overlayed F
An RP layer was obtained. (1-A-)

After demolding, a bathtub with a stationary washing place in which the gel coat layer, the intermediate layer, the back layer and the FRP layer are integrated (1
-A-).

The obtained bathtub with a stationary washing room (1-A-
) Satisfies the performance of JIS A 5712 (bathtub with glass fiber reinforced polyester washroom),
It was effective in shortening the work time and the number of workers. The evaluation results are shown in Table-1.

Comparative Example-1 (Molding of FRP layer) The FRP layer was molded in the same manner up to the adhesion of the reinforcing material of Reference Example-1. Unsaturated polyester resin polylite LP-
821-N (manufactured by Dainippon Ink and Chemicals, Inc.) 100
Part, 50 parts of Permek N N 1.0 part, 1-inch long glass roving ER2310SP-10 (manufactured by Asahi Fiber Glass Co., Ltd.) was sprayed up on the above-mentioned molded article (1-) coated with a gel coat, and after impregnation with a roll, 60 ° C
After curing for 30 minutes, a FRP layer with an overlay of about 2 mm was obtained. (1-B-)

After demolding, a bathtub with a stationary washing place in which the gel coat layer, the intermediate layer, the back layer and the FRP layer are integrated (1
-B-)

The obtained bathtub with a stationary washing room (1-B-
) Satisfied the performance of JIS A 5712, but required a long working time and required a large number of personnel.
The evaluation results are shown in Table 1.

[0043]

[Table 1]

Reference Example-2 (Molding of Artificial Marble Bathtub) An artificial marble bathtub was prepared using a generally known casting and room temperature curing system by using a vinyl ester resin and a stone tone filler. (2-)

Example-2 (Molding of FRP layer) Unsaturated polyester resin "Polylite FS-150"
90 parts (manufactured by Dainippon Ink and Chemicals, Inc.) was mixed with 0.1 part of dimethylaniline and 10 parts of styrene monomer to obtain unsaturated polyester resin A-2.

Hollow filler "D" was added to 100 parts of A-2.
UALITE M6017AE (PIERCE & STE
13% by volume, 15 parts of talc SW (manufactured by Nippon Talc Co., Ltd.) as a thixotropic agent, and 60 parts of filler "calcium carbonate NS-100 (manufactured by Nitto Koka Co., Ltd.)". Then, the mixture was stirred to obtain a resin compound C-2.

The obtained resin compound C-2 had a viscosity of 17.0 poise, a thixotropic property of 4.5, and a gelation time of 3 minutes (JIS K
6901 4,8).

Permek N for 100 parts of C-2
1.0 part, 16mm long glass roving "ER231
25 parts of "0SP-10 (manufactured by Asahi Fiber Glass Co., Ltd.)" was sprayed up into an artificial marble bath (2-), and the roll impregnation step was not performed, after-curing was performed at 60 ° C for 30 minutes, and the overlayed FRP was formed with a thickness of about 1 mm. An artificial marble bath having layers was obtained. (2-A-)

The obtained artificial marble bathtub (2-A-) is
The performance was satisfactory, and it was effective in shortening the work time and reducing the number of personnel. The evaluation results are shown in Table 2.

Example-3 (molding of FRP layer) The procedure up to the molding of the artificial marble bath of Reference Example-2 was performed in the same manner,
The FRP layer was molded.

Unsaturated polyester resin "Polylite 80"
10 (manufactured by Dainippon Ink and Chemicals, Incorporated) "100 parts" against thixotropic agent "silica powder, Reorosil QS-"
20 (manufactured by Tokuyama Soda Co., Ltd.) ", 2.5 parts, 0.4% of 6% cobalt naphthenate, 0.1 part of dimethylaniline and 45 parts of styrene monomer are mixed to obtain an unsaturated polyester resin A-3. It was

Next, unsaturated polyester resin A-110
Hollow filler "DUALITE M6017A" for 0 parts
E (manufactured by PIERCE & STEPN) "7.5% by volume
Were mixed to obtain a resin compound C-3.

The obtained resin compound C-3 had a viscosity of 28.0 poise, thixotropic property of 5.6 and gelation time of 3 minutes (JIS K
6901 4,8).

Permek N for 100 parts of C-3
1.0 part, 16 mm long glass roving ER2310S
Twenty-five parts of P-10 (manufactured by Asahi Fiber Glass Co., Ltd.) was applied to the artificial marble bath (2-) without performing the roll impregnation step,
After curing at 60 ° C. for 30 minutes, an artificial marble bath having an FRP layer overlaid with a thickness of about 1 mm was obtained. (3-A-)

The obtained artificial marble bathtub (3-A-) is
The performance was satisfied, and it was effective in shortening the work time and reducing the number of personnel. The evaluation results are shown in Table 2.

Example-4 (molding of FRP layer ) The procedure up to the molding of the artificial marble bath of Reference Example-2 was carried out in the same manner,
The FRP layer was molded. Unsaturated Poles of Example-1
Hollow filler "DUAL" for 100 parts of Tell Resin A-1
ITE M6017AE (PIERCE & STEPN
15.0% by volume, filler "calcium carbonate NS"
After adding 80 parts of -100 (manufactured by Nitto Koka Co., Ltd.), stir
Thus, a resin compound C-4 was obtained. Obtained resin con
Pound C-4 has a viscosity of 23.0 poise, thixotropic 5.1.
The gelation time was 3 minutes (JIS K 6901 4,8).

Permek N for 100 copies of C-4
1.0 part, 16 mm long glass roving ER2310S
25 parts of P-10 (made by Asahi Fiber Glass Co., Ltd.)
Apply to the stone bath (2-) and do not perform the roll impregnation process,
After curing at 60 ° C for 30 minutes, over about 1mm thick
-A synthetic marble bathtub with a laid-up FRP layer
Obtained. (4-A-)

[0058] The artificial marble bathtub (4-A-) obtained is
It satisfies the performance, shortens the working time,
It was effective for reduction. The evaluation results are shown in Table 3.
It was

Comparative Example-2 (Molding of FRP layer) FRP was the same until the artificial marble bath of Example-2 was molded.
The layers were molded. To 100 parts of unsaturated polyester resin "Polylite LP-821-N (manufactured by Dainippon Ink and Chemicals, Inc.)", Permeck N 1.0 part, 1 part
50 parts of inch-long glass roving ER2310SP-10 (manufactured by Asahi Fiber Glass Co., Ltd.) was sprayed up into the artificial marble bath (2-), and after the roll impregnation step, 60
After curing at 30 ° C. for 30 minutes, an artificial marble bath having an FRP layer overlaid with a thickness of about 1 mm was obtained. (2-B-)

The artificial marble bath (2-B-) obtained was
Although it satisfied the performance, it required a long working time and required a large number of workers. The evaluation results are shown in Table 2.

[0061]

[Table 2]

[0062]

The advantage of the present invention is that when forming an FRP layer for reinforcing or thickening a molded article such as plastic, it is possible to omit the impregnation defoaming step which conventionally had to rely on manual work. However, the process after spraying is almost unnecessary.

That is, the molding process of the FRP layer can be greatly simplified, the molding time can be shortened, and the number of workers can be reduced. Also, since the roll impregnation step is unnecessary,
It has the merit that the gelling time of the resin can be set extremely short and the process can be immediately moved to the next step.

Further, the FRP layer molding according to the present invention can be automated by a robot and the like, and it is possible to eliminate manpower in a working environment in which a monomer odor drifts, and to obtain an excellent effect in hygiene. that's all

Claims (6)

[Claims] 1. A composition comprising an unsaturated polyester resin or a vinyl ester resin and / or a vinyl ester resin containing a spherical hollow filler and a thixotropic agent on one surface of a molded article made of an unsaturated polyester resin or a vinyl ester resin, and a fiber. A method for molding a fiber-reinforced plastic, which comprises spraying a reinforcing material and curing it. 2. An unsaturated polyester resin and / or vinyl ester resin solution containing a spherical hollow filler and a thixotropic agent has a viscosity of 10 to 50 poise (JIS K 690).
The molding method according to claim 1, which is 1). 3. The thixotropic property of an unsaturated polyester resin and / or vinyl ester resin solution containing a spherical hollow filler and a thixotropic agent is 4 to 9 (JIS K-6901). Item 1. The molding method according to Item 1. 4. The molding method according to claim 1, wherein the spherical hollow filler has a diameter of 10 to 300 μm and a specific gravity of 0.02 to 0.8. 5. A spherical hollow filler having a content of 5. in an unsaturated polyester resin and / or vinyl ester resin liquid.
It is 0-60 volume%, The molding method of Claim 1 characterized by the above-mentioned. 6. A fiber-reinforced plastic molded product obtained by the molding method according to claim 1.