JP3265730B2 - Reinforcement method and molded product thereof - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a resin
By spraying up a composition containing a specific unsaturated polyester resin or vinyl ester resin, a method for reinforcing a resin molded product characterized by being cured, in particular, a thermosetting, or thermoplastic acrylic resin The present invention relates to a method for reinforcing an artificial marble bath, a kitchen countertop, a bay window, a whirlpool, etc., obtained by a molding method such as casting, pressing, vacuum forming, pressure forming, etc., as a matrix resin, and a molded product obtained by the method.

[0002]

2. Description of the Related Art Conventionally, thermosetting acrylic resin molded articles such as artificial marble bathtubs, kitchen countertops, bay windows, etc. obtained by casting, press molding, and resin injection molding methods are composed of a surface layer, an intermediate layer, To obtain impact resistance that can withstand construction and use, hand lay-up,
In general, partial reinforcement or local thickening by spray-up is performed.

Further, a thermoplastic acrylic resin molded product such as whirlpool obtained by vacuum molding or the like does not have sufficient rigidity to withstand use alone, and in most cases, it is increased in thickness and rigidity by a reinforcing layer. Such a reinforcing layer is usually partially formed by hand lay-up or spray-up molding.

[0004] The reinforcement and thickening processes by hand lay-up and spray-up molding referred to here are the former: a chopped strand mat having a fiber length of about 2 inches;
It is a general method to impregnate a thermosetting resin into a chopped strand of about 1 inch using a defoaming roller and to cure the resin.

[0005] At this time, in the case of a molded article having a complicated shape, the impregnating and defoaming step, particularly for the details, requires careful work by hand. Such a reinforcing step consumes most of the entire molding time and has also become the rate-limiting of the molding cycle.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide an impregnating and defoaming step which spends most of the entire molding time in the reinforcing and thickening steps performed by the conventional hand lay-up and spray-up molding methods. The present invention is directed to a reinforcing method that saves labor and reduces labor involved, simplifies the reinforcing process, and enables a longer molding cycle.

[0007]

Means for Solving the Problems As a result of intensive studies, the present inventors have overcome the above-mentioned problems with a specific resin composition and completed the present invention.

That is, the present invention relates to a thermosetting or thermoplastic resin.
Spraying a composition containing an unsaturated polyester resin and / or a vinyl ester resin containing a spherical hollow filler and a thixotropic agent and a fiber reinforcing material on the back surface of the reactive acrylic resin molded product, and curing , Composition viscosity
Is 10 to 50 poise (JIS K-6901), and
And the thixotropic property of the composition is 4 to 9 (JIS K-6901 4.5)
In which it relates to a method for reinforcing a resin molded product, characterized in, and a molded article thereof (except panel) that. Preferably, the hollow filler has a diameter of 10 to 300 microns and a specific gravity of 0.1.
02 to 0.8, preferably the resin composition contains an α, β-unsaturated monomer, and the content of the hollow filler is preferably 5 to 60% by volume in the resin composition. And a thermosetting or thermoplastic acrylic resin molded product (excluding a panel) thus obtained.

According to the present invention, an unsaturated polyester resin and / or a vinyl ester resin containing a fiber reinforcing material, a spherical hollow filler and a thixotropic agent on the back surface of a thermosetting or thermoplastic acrylic resin molded product. By spraying the composition containing, it is possible to complete the impregnation defoaming step with almost no need for labor, to provide impact resistance and rigidity that can withstand transportation, construction and use, to provide thickness, and to save the power of molded articles. And it enables rapid production.

Further, the reinforcing method of the present invention will be described in detail.

The resin molded article of the present invention is a molded article requiring rigidity and having a thickness of about 0.01 to 20 mm, and may have any shape . A thermosetting or thermoplastic acrylic resin molded product, the molded product is cast, pressed,
This means a semi-finished product obtained by an existing molding method such as vacuum molding and pressure molding. Acrylic resin is an existing resin used for manufacturing artificial marble bathtubs, kitchen countertops, bay windows, whirlpools, and the like.

The unsaturated polyester resin used for forming the reinforcing layer of the present invention is preferably an unsaturated dibasic acid or an anhydride thereof, or a saturated dibasic acid or an anhydride thereof, and a glycol or carbon number. A resin obtained by a dehydration-condensation polymerization reaction with 2-3 alkylene oxides is converted to an α, β-unsaturated monomer such as styrene, α-methylstyrene, methyl methacrylate, ethyl methacrylate, and β-hydroxyethyl methacrylate. Is dissolved in

The vinyl ester resin 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, and reacting styrene, α-methylstyrene, Methyl methacrylate, ethyl methacrylate, β
-It is dissolved in an α, β-unsaturated monomer such as hydroxyethyl methacrylate. The α, β-unsaturated monomer may be further added in order to bring the viscosity of the composition to 10 to 50 poise for spray-up.

The spherical hollow filler of the present invention is not particularly limited, and generally known ones can be used. The material is inorganic such as glass, silica and ceramic, vinylidene chloride, acrylic There is no particular limitation on organic materials such as acryl-acrylonitrile copolymers, and surface-treated materials. Preferably, the particle size is desirably large enough to pass through a spray-up machine nozzle, preferably 10-300 microns, more preferably 15-200 microns, and its true specific gravity is preferably 0.02-0. It is about 8, and the value is greatly different between inorganic and organic substances. Also, the pressure resistance is preferably higher in order to prevent breakage during mixing and molding. Its strength is preferably 5 to 1000 kg / cm ² , particularly preferably 1 to 1000 kg / cm ² .
00 kg / cm ² or more.

As commercial products, for example, Scotch Light Glass Bubble (manufactured by Sumitomo 3M Limited), MIRALITE,
MICRLITE, Dualite (PIERCE & S
TEVENS), Glass Microballo
on (manufactured by EMERSPON & CUMING), QC
EL, Microcel (manufactured by Asahi Glass), Expancel, Microcel (manufactured by Nippon Philite), MFL
A product such as -80CA (manufactured by Matsumoto Yushi Co., Ltd.) can be used.

The amount of the hollow filler to be added is preferably 5.0 to 60% by volume (in the composition), more preferably 7.
0 to 50% by volume (in the composition).

The thixotropic agent of the present invention is not particularly limited to a star-like, needle-like, whisker-like, or adjacent piece-like shape, and has a shape that imparts thixotropic properties to a thermosetting resin. I just want it. Specific examples include, for example, silica powder,
Examples include talc powder, glass flakes, metal whiskers, ceramic whiskers, calcium sulfate whiskers, asbestos, smectite, and the like. If necessary, two or more of the above may be used in combination.

Commercially available thixotropic agents include, for example, Leoloseal QS series (manufactured by Tokuyama Soda Co., Ltd.) and Aerosil series (manufactured by Nippon Aerosil Co., Ltd.)
X series (manufactured by Wilbur Ellis), FRANNKL
IN FIBER (USG), Talc SW, SS,
SWE, (manufactured by Nippon Talc), talcan powder PK,
Rotalcoo T (manufactured by Hayashi Kasei), Albolex YS
(Manufactured by Shikoku Chemical Industry Co., Ltd.).

The size of the thixotropic agent may be any size as long as it can pass through the nozzle of the spray-up machine. The addition amount is preferably 1 to 20 parts by weight (based on the resin composition). It may be increased or decreased within the above range depending on the ability to impart denaturation.

The curing catalyst is not particularly limited, and generally known ones can be used. For example, methyl ethyl ketone peroxide, cyclohexane peroxide, acetylacetone peroxide, acetoacetate peroxide, benzoyl peroxide and the like can be used. A peroxide catalyst may be used, 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.

Examples of the curing accelerator include metal salts of organic acids and chelates, such as cobalt naphthenate, cobalt octylate, cobalt acetylacetone, and the like.
Alternatively, amines such as dimethylaniline and diethylaniline may be used, and two or more of these may be used in combination. The addition amount is preferably 0.01 to 5 parts by weight based on 100 parts by weight of the composition.

If necessary, an antifoaming agent, a modifier and the like may be added to the composition.

The fiber reinforced material of the present invention is, for example, glass fiber, aramid fiber, vinylon fiber, polyester fiber, nylon fiber, carbon fiber, metal fiber, or a combination thereof. Preferred are glass fibers and carbon fibers. The form of the fiber is preferably a string shape or a roving shape. It is also possible to cut a string-like or roving-like thing into a length of 3 to 25 mm in advance and use it as a chopped strand. The preferred fiber length is 3 to 50 mm, particularly preferably 3 to 25 mm. The fiber reinforcement, usually in the case of spray-up molding, is sprayed with the composition and applied to a substrate. However, each spray nozzle is a separate mouth.

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

The composition of the unsaturated polyester resin and the vinyl ester resin of the present invention may contain a pigment,
You may mix | blend other fillers, a low-shrinking agent, etc. What is necessary is just to add the thing for unsaturated polyester resins of a general market as a pigment and a low-shrinking agent.

The other filler is 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, and the like. The particle size may be a size that can pass through the spray-up machine. Further, two or more of these may be used in combination.

Further, the composition of the unsaturated polyester resin or vinyl ester resin containing spherical hollow fillers and thixotropic imparting agents used in the present invention, viscosity 10-50 poise, preferably a viscosity 10-30 poise (JIS -K-
A 6901 4,5), thixotropy, 4.0 to 9.0,
Preferably 4.0 to 7.0 (JIS-K-69014,
5), and the gelation time is preferably 2 to 5 minutes (JIS
-K-6901 4,8). Viscosity and thixotropic
Outside of this range, spray-up molding becomes difficult, which is not preferred.

The molded articles to which the reinforcing method of the present invention can be applied include an acrylic molded article, a cast bathtub,
There are press artificial marble bathtubs , vanities , kitchen kitchen components, electric appliances, automobile parts, thermoplastic acrylic vacuum molded products, and the like, and are not particularly limited.

The FRP spray-up reinforcement method of the present invention comprises:
A composition containing an unsaturated polyester resin and / or a vinyl ester resin containing a spherical hollow filler and a thixotropic agent of the present invention using a commercially available spray gun and a chopper, and a fiber reinforcing material having a length of 3 to 25 mm. Is sprayed onto one surface of a resin molded product, preferably a thermoplastic or thermosetting acrylic resin molded product, and cured.

[0030]

EXAMPLES The present invention will be described in detail with reference to Synthesis Examples, Examples and Comparative Examples, where "parts" and "%" are on a weight basis.

Reference Example 1 (Formation of Acrylic Artificial Marble Bathtub) An acrylic artificial marble bathtub (referred to as 1-) was prepared by using a publicly known casting and room temperature curing system using an acrylic syrup and a grain-like filler. did.

Example 1 (Preparation and Reinforcement of Composition for Forming Reinforcing Layer) Unsaturated polyester resin (trade name: Polylite 801)
0, 100 parts of Dainippon Ink and Chemicals, Inc.), 2.5 parts of thixotropic agent (silica powder, trade name: Leolosil QS-20, manufactured by Tokuyama Soda Co., Ltd.), 6% cobalt naphthe 0.4 part of catenate, 0.1 part of dimethylaniline,
50 parts of a styrene monomer were mixed to obtain an unsaturated polyester resin A-1.

Next, the unsaturated polyester resin A-110
0 part for spherical hollow filler (trade name: DUALITE)
M6017AE, PIERCE & STEVEN) 1
6% by volume, 10 parts of a thixotropic agent (trade name: Talc SW, manufactured by Nippon Talc Co., Ltd.), filler (calcium carbonate,
After adding 70 parts (trade name: NS-100, manufactured by Nitto Powder Co., Ltd.), the mixture was stirred to obtain a resin composition C-1.

The obtained resin composition C-1 had a viscosity of 18.
0 poise, thixotropic 5.6, gelation time 4 minutes (JIS K 6901 4,8)
Met.

C-1 Permecco N for 100 parts
(Methyl ethyl ketone peroxide, curing catalyst, manufactured by NOF Corporation) 1.0 part, 16 mm long glass roving G
25 parts of R31 (manufactured by Nippon Sheet Glass Co., Ltd.) was sprayed up on the back surface of the acrylic artificial marble bath (1-), and after-curing at 60 ° C. for 30 minutes without performing the roll impregnation step, to obtain a reinforcing layer having a thickness of about 1 mm. (1-A-)

Example 2 (Supplement of Acrylic Artificial Marble Bathtub)
Strong layer molding) 100 parts of the unsaturated polyester resin A-1 of Example-1
Against spherical hollow filler (trade name: DUALITE M6)
017AE, PIERCE & STEVEN) 16
% And calcium carbonate (trade name: NS-100, Nitto
After adding 80 parts of Powder Chemical Co., Ltd. and stirring, the resin composition is stirred.
C-3 was obtained. The obtained resin composition C-3 has a viscosity of 2
3.0 poise, thixotropic 5.1, gelation time 3 minutes (JIS K 6901
4,8).

Except for using the resin composition C-3,
Spray on the back of acrylic marble bath (1-)
30 minutes at 60 ° C without roll impregnation
The mixture was turqued to obtain a reinforcing layer having a thickness of about 1 mm. (3-A-
)

Forming a reinforcement layer on an acrylic artificial marble bath
Table 1 shows the evaluation results.

Comparative Example 1 (Formation of Reinforcement Layer) A reinforcement layer was formed in the same manner as in Example 1 up to the formation of the acrylic artificial marble bath.

For 100 parts of an unsaturated polyester resin (trade name: Polylite LP-821-N, manufactured by Dainippon Ink and Chemicals, Inc.), 1.0 part of Permeccu N, 1 inch long glass roving (ER2310SP-10) , Made by Asahi Fiber Glass Co., Ltd.) spray up 50 parts into acrylic artificial marble bath (1-)
After-cure was performed at 30 ° C. for 30 minutes to obtain a reinforcing layer having a thickness of about 1 mm. (1-B-) A reinforcing layer was formed on an acrylic artificial marble bath and the results of the evaluation are shown in Table 1.

[0041]

[Table 1]

Reference Example-2 (Vacuum forming of thermoplastic acrylic plate) An acrylic sheet [LUCITE X manufactured by Dupont]
L] to form a whirlpool (2-) 1
750 x 1100 x 450 mm was obtained.

Example 3 (Formation of reinforcing layer of whirlpool (vacuum molded product of thermoplastic acrylic plate)) 90 parts of an unsaturated polyester resin (Polylite FS-150, manufactured by Dainippon Ink and Chemicals, Inc.) 0.1 part of dimethylaniline and 10 parts of a styrene monomer were mixed to obtain an unsaturated polyester resin A-2.

A-2 100 parts of spherical hollow filler (DUALITE M6017AE, PIERCE & S)
13% by volume of TEVEN, a thixotropic agent (trade name:
15 parts of talc SW, manufactured by Nippon Talc Co., Ltd.) and 60 parts of a filler (calcium carbonate, trade name: NS-100, manufactured by Nitto Powder Co., Ltd.) are added, followed by stirring and then a resin composition C-2.
I got

The obtained resin composition C-2 had a viscosity of 17.
0 poise, thixotropic 4.5, gelation time 3 minutes (JIS K 6901 4,
8). C-2, permek N for 100 copies
1.0 part, 16mm long glass roving (ER2310
25 parts of SP-10 (manufactured by Asahi Fiberglass Co., Ltd.) were sprayed up into a whirlpool (2-), cured at room temperature without performing a roll impregnation step, and a reinforcing layer overlaid with an FRP layer having a thickness of about 2 mm was obtained. . (2-A-)

Example 4 (whirlpool (thermoplastic
Reinforced layer molding of vacuum-molded product of ril plate) 100 parts of unsaturated polyester resin A-1 of Example-1
Against spherical hollow filler (DUALITE M6017A)
E, PIERCE & STEVEN) 8% by volume
Thereafter, stirring was performed to obtain a resin composition C-4.

The obtained resin composition C-4 had a viscosity of 17.
0 poise, thixotropic 4.5, gelation time 4 minutes (JIS K 6901 4,
8). Same except that C-4 was used for the resin composition
Spray up on the back of the whirlpool (2-)
And cured at room temperature without performing the roll impregnation process.
A reinforcement layer overlaid with the FRP layer was obtained.
(4-A-) Reinforcement layer on thermoplastic acrylic whirlpool
Was formed, and the evaluation results are shown in Table-4.

Comparative Example 2 (Formation of Reinforcement Layer) Unsaturated polyester resin (trade name: Polylite LP-9)
100 parts of 24-N, manufactured by Dainippon Ink and Chemicals, Inc., and 100 parts of Permecc N, 50 parts of 1-inch long glass roving (trade name: ER2310SP-10, manufactured by Asahi Fiberglass Co., Ltd.) It was sprayed up to the pool (2-), cured at room temperature through a roll impregnation step, and an FRP reinforcing layer having a thickness of about 2 mm was obtained. (2-B-) A reinforcing layer was formed on a thermoplastic acrylic whirlpool, and the evaluation results are shown in Table-2.

[0049]

[Table 2]

[0050]

An advantage of the present invention is that, when forming a reinforcing layer made of FRP, the impregnation defoaming step which had to rely on manual work can be omitted, and the step after spraying is almost unnecessary. It is in. In other words, the molding process of the reinforcing layer can be greatly simplified, thereby shortening the molding time,
The number of working personnel can be reduced. Also, since the roll impregnation step is unnecessary, the gel time of the resin can be set extremely short,
It has the advantage that the process can be promptly shifted to the next step. In addition, the FRP reinforcement layer molding can be automated by robots, etc., eliminating human labor from the work environment where monomer odor drifts,
Excellent effects are also obtained in hygiene.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI B29K 105: 06 B29L 9:00 105: 16 31:44 B29L 9:00 B29C 67/14 E 31:44 67/16 (56) References JP-A-50-45871 (JP, A) JP-A-2-95832 (JP, A) JP-A-2-227219 (JP, A) JP-B-54-8702 (JP, B1) (58) Survey Field (Int.Cl. ⁷ , DB name) B29C 70/00-70/88 A47K 4/00 A47K 3/00-3/40

Claims (4)

(57) [Claims] 1. A composition comprising an unsaturated polyester resin and / or a vinyl ester resin containing a spherical hollow filler and a thixotropic agent and a fiber reinforced material on the back surface of a thermosetting or thermoplastic acrylic resin molded product. And the composition is cured, and the viscosity of the composition is 10 to 50.
A method for reinforcing a resin molded product, which is a poise (JIS K-6901), and wherein the thixotropic property of the composition is 4 to 9 (JIS K-6901 4.5). 2. The spherical hollow filler has a diameter of 10 to 300.
2. The reinforcing method according to claim 1, wherein the reinforcing material has a micron and a specific gravity of 0.02 to 0.8. 3. The reinforcing method according to claim 1, wherein the content of the spherical hollow filler is 5.0 to 60% by volume in the unsaturated polyester resin and / or vinyl ester resin composition. 4. A molded article having a reinforcing layer obtained by the reinforcing method according to any one of claims 1 to 3 and having a thermosetting or thermoplastic acrylic resin on a surface layer (excluding a panel).