JP3200920B2 - Resin composition and FRP spray-up molding method using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel and useful resin composition and an FRP spray-up molding method using the resin composition. More specifically, the conventional F
The present invention relates to a novel resin composition capable of omitting an impregnation defoaming operation by a roller in an RP spray-up molding method, and a novel FRP spray-up molding method using the same.

[0002]

2. Description of the Related Art In a spray-up molding method, which is a conventional FRP molding method, a thermosetting resin and a fiber reinforcing material having a length of about 25 mm are applied by a spray-up machine.
It is a well-known method in which it is held by a human hand, impregnated and defoamed by a roller or the like, hardened, and then released to obtain an FRP molded product.

Among the spray-up molding methods, Japanese Patent Application Laid-Open No. 50-45871 discloses a technique of omitting the impregnation and defoaming operation using such a roller.
An inert non-absorbent powder having a particle size passing through a screen of 0 to 300 mesh and an unsaturated polyester resin are mixed at a volume ratio of 3: 7 to 3: 1. A method is disclosed in which a mixture and glass fiber particles are applied using a spray-up machine at a weight ratio of 3: 1 to 8: 1.

[0004]

However, in the conventional spray-up molding method, it is very difficult to omit the impregnation defoaming operation using a roller or the like.
Even if it can be omitted, a large number of large bubbles are present or the resin and the fiber reinforcing material slip down before curing, so that a satisfactory FRP molded product cannot be obtained.

The method disclosed in Japanese Patent Application Laid-Open No. 50-45871 discloses an unsaturated polyester resin, a marble powder (calcium carbonate) of about 40 to 300 mesh, silica sand or talc (talc). And a filler having a high specific gravity is mixed with a sprayable unsaturated polyester resin at a volume ratio of 3: 7 to 3: 1. : 1 to 8:
Spraying onto a supporting surface at a weight ratio of one.

[0006] However, such a method is the same as that commonly used in a septic tank or the like.
Since the viscosity of the resin mixture increases, the impregnation and defoaming operation using a roller or the like becomes difficult, and after all, the impregnation defoaming operation using such a roller or the like cannot be omitted.

Further, if the weight ratio of the mixture and the glass fiber particles is set to around 8: 1, the mixture and the glass fiber particles are shifted and fall, and an FRP molded product cannot be obtained.

[0008] Even if a flat plate can be formed, the strength is extremely reduced, and it cannot be used as a structural member or a reinforcing member. Naturally, an FRP molded product having a three-dimensional shape cannot be obtained.

As described above, as long as the conventional technique is followed, omitting the impregnation and defoaming operation using a roller or the like is itself a place that causes a great inconvenience, and therefore, omitting such operation is extremely difficult. I can say that.

[0010]

Means for Solving the Problems Accordingly, the present inventors have:
In order to solve the above-mentioned problems, as a result of intensive studies, a specific resin composition comprising a thermosetting resin, a spherical hollow filler, and a star-shaped filler When a material and a fiber reinforced material having a length of 3 to 25 mm are applied using a spray-up machine, the impregnation and defoaming operation using such rollers as a problem in the FRP spray-up molding method is completely performed. The present invention has been completed by finding that it can be omitted.

That is, the present invention basically provides a thermosetting resin (A), a spherical hollow filler (B), and a star-shaped filler (excluding mica powder) (C) The weight ratio of (A): filler (B): filler (C) is 99.5: 0.
It is intended to provide a specific resin composition for spray-up molding (but not containing mica powder), which is to be contained at a ratio of 5: 0 to 80.0: 5.0: 15.0. Yes, in addition, the resin (A), the filler (B), and the filler (C) are essential components.
Another object of the present invention is to provide an FRP spray-up molding method comprising applying a specific resin composition (but not containing mica powder) and a fiber reinforcing material using a spray-up machine.

[0012] More specifically, the specific resin composition was bovine this
By simply applying a fiber reinforcement and a specific fiber reinforcement having a length of 3 to 25 mm using a spray-up machine at the same time, that is, without performing impregnation and defoaming work with a roller, etc. It is also an object of the present invention to provide an FRP spray-up molding method comprising obtaining an FRP molded product.

[0013]

[Constitution] Here, first, the resin composition of the present invention (however,
And mica powder-free) comprises a thermosetting resin (A), a spherical hollow filler (B), and a star-shaped filler (excluding mica powder) (C). , Resin (A):
Filler (B): The weight ratio of filler (C) is 99.
5: 0.5: 0 to 80.0: 5.0: 15.0.

[0014] Next, the FRP spray-up molding method of the present invention provides a spray-up machine for simultaneously using such a specific resin composition and a fiber reinforcing material, preferably a fiber reinforcing material having a length of 3 to 25 mm. Is applied to obtain an FRP molded product.

By adopting such a configuration, FR
In the P spray-up molding method, the impregnation defoaming operation using a roller or the like can be omitted for the first time and completely, providing a new and useful resin composition, and using the resin composition to be new and useful. This makes it possible to provide a spray-up molding method.

First, the thermosetting resin (A) used in the present invention is not particularly limited, and generally known and commonly used resins can be used. Among them, particularly typical ones are exemplified by unsaturated polyester resins or vinyl ester resins.

Preferably, the unsaturated monomer having an ethylenically unsaturated bond is contained in an amount of 40 to 70% by weight and further contains a thixotropic agent, a curing accelerator or an antifoaming agent. belongs to.

Next, the spherical hollow filler (B) used in the present invention is not particularly limited, and generally known and commonly used ones can be used.

The material of the filler may be inorganic, such as glass, silica, or ceramic, or organic, such as vinylidene chloride, or may be surface-treated. There is no particular limitation.

The particle size may be any size as long as it can pass through a spray-up machine.
It is appropriate to be within the range of 00 microns (μm), and its true specific gravity is about 0.02 to 0.6. This value differs greatly depending on whether it is inorganic or organic. Further, the pressure resistance is preferably higher in order to prevent breakage during mixing or during molding.

At present, as a commercially available product of the filler (B), for example, "Scotchlite glass bubble"
[Sumitomo 3M Corporation products], "MIRALIT
E ”,“ MICRITE ”or“ Dualit ”
e] [Pierres and Stevens (PIERC)
E & STEVENS CHM products], "Glass Microball (Glass Microball)
oon)] [Emmerspond and Coming (EME
RSPON & CUMING) products], "Q-CE
L ”or“ Microcell ”
[Asahi Glass Co., Ltd. product] or “Expancel” or “Microcell” (a product of Nippon Philite Co., Ltd.) can be used.

[0022] The amount of the filler (B) to be added is 0.
The range of 5 to 5.0 parts by weight (based on the resin composition) is appropriate, and the range is increased or decreased depending on the true specific gravity of the filler (B).

Further, the above-mentioned star-like filler (C) used in the present invention is simply represented by a star shape, and the shape thereof includes a star shape, a needle shape and the like. And whisker-like or adjacent piece-like shapes, but are not particularly limited, as long as the shape can impart thixotropic properties to the above-mentioned thermosetting resin (A).

If only typical representative examples of the filler (C) are given as examples, talc powder , glass free
Over click, metal whisker, ceramic whisker or sulfate of calcium whiskers and the like.

The size of the filler (C) may, of course, be such that it can pass through a spray-up machine. Further, the amount of the filler (C) added may be as follows:
The range of 0 to 15 parts by weight (based on the resin composition) is appropriate, and the amount is increased or decreased within the range depending on the ability of the filler (B) to impart thixotropic properties.

Further, the curing catalyst used in the present invention is not particularly limited, and generally known and commonly used ones can be used. Among them, only typical ones are exemplified. If it is a peroxide catalyst such as methyl ethyl ketone peroxide, cyclohexane peroxide, acetylacetone peroxide, acetoacetate peroxide or benzoyl peroxide, these may be used alone or in combination of two or more. Is, of course.

The curing accelerator used in the present invention is, for example, a metal salt of an organic acid, particularly a cobalt salt or an amine, and particularly a typical example thereof. Examples are only cobalt salts such as cobalt naphthenate, cobalt octylate or cobalt acetylacetone; and various amines such as dimethylaniline or diethylaniline, which may be used alone. Of course, two or more of them may be used in combination.

Further, the fiber reinforcing material used in the present invention is, for example, glass fiber, aramid fiber, vinylon fiber, polyester fiber, nylon fiber, carbon fiber or metal fiber, or a combination thereof.

Particularly preferred are glass fibers,
For example, carbon fiber or organic fiber. In addition, the form of these fibers is preferably a string shape or a roving shape, and such a string shape or a roving shape is cut in advance into a length of 3 to 25 mm,
It is also possible to use chopped strands.

The weight ratio of the fiber reinforcing material is preferably within the range of 10 to 30% by weight in the molding material, more preferably within the range of 10 to 25% by weight. is there.

Further, it is a matter of course that the resin composition of the present invention may further contain a pigment, a general filler or a low-shrinking agent, if necessary. Among them, first, any of the above-mentioned pigments may be used as long as they are generally commercially available for unsaturated polyester resins.

Next, the above-mentioned general fillers are used for the purpose of increasing the amount of raw materials, and if only typical ones among them are exemplified,
Calcium carbonate, silica, glass, alumina, clay,
It is a so-called powdery material such as aluminum hydroxide, barium sulfate, calcium sulfate or silica stone, and its particle size may be any size as long as it can pass through a spray-up machine. These may be used alone or in combination of two or more.

Further, as the above-mentioned low-shrinking agent, it is appropriate to use what is called a thermoplastic resin, and specific examples thereof include methyl methacrylate, ethyl methacrylate, butyl methacrylate, and methyl methacrylate. Various lower alkyl esters of (meth) acrylic acid, such as acrylate or ethyl acrylate;

Alternatively, at least one of the above-mentioned vinyl monomers, including homopolymers or copolymers of various vinyl monomers such as styrene, vinyl chloride and vinyl acetate. , Lauryl methacrylate, isovinyl methacrylate, acrylamide, methacrylamide, hydroxylalkyl-acrylate or -methacrylate, acrylonitrile, methacrylonitrile, acrylic acid, methacrylic acid, and at least one monomer selected from the group consisting of cetylstearyl methacrylate Copolymers with the class;

And cellulose acetate butyrate or cellulose acetate propionate,
Various cellulose derivatives; or various polyolefins, such as polyethylene or polypropylene,
These are particularly typical, and these may be used alone or in combination of two or more.

The above-mentioned FRP spray-up molding method referred to in the present invention means that the thermosetting resin composition of the present invention is mixed with a fiber having a length of 3 to 25 mm by using a commercially available spray-up machine. With this spray-up machine, the reinforcing material is only applied to the forming die or the support, and is cured without performing any impregnation and defoaming work with a roller or the like. It refers to a method for obtaining a composite molded article.

Of course, it may be used as a lining material for a structure.

[0038]

Next, the present invention will be described based on Examples and Comparative Examples.
Although described more specifically, hereinafter, unless otherwise specified, all “parts” and “%” are based on weight.

Example 1 [Blending of resin composition (UP-1)] First, "DUALITE" was added to 98 parts of "Polylite FS-150" (an unsaturated polyester resin manufactured by Dainippon Ink and Chemicals, Inc.).
M6017AE ”(PIERCE & STEVEN
2 parts of a spherical hollow filler (manufactured by Company S) were mixed to obtain an intended resin composition.

[Spray-up molding] Using a commercially available spray-up machine for FRP, the resin composition (UP-1)
“ER2310S” cut into 5 parts and a length of 16 mm
P-10 "[glass roving manufactured by Asahi Fiberglass Co., Ltd.] and" Permec N "at a ratio of 1.0% to the resin composition [cured by NOF Corporation 55% MEKPO] with an L-shaped mold (height = 500 mm, width = 500
mm and length = 1,000 mm) and cured, then 400 mm high and 400 mm wide
F is 800 mm long and 3 mm thick
An RP molded product (FRP-1) was obtained.

At this time, no impregnation and defoaming operation using a roller or the like was performed at all.

Example 2 [Blending of Resin Composition (UP-2)] "Polylite FS"
-150 ”in 93 parts,“ DUALITE M6017
AE ”and“ Franklin Fiber (FRA)
NKLINFIBER) A-30] [UNITED STATES GYPS
UM), and the desired resin composition was obtained.

[Spray-up molding] In the same manner as in the spray-up molding of Example 1, 80 parts of the resin composition (UP-2) and 20 parts of a glass roving having a length of 16 mm were used.
Part and a curing agent having a ratio of 1.0% with respect to the resin composition, an intended FRP molded product (FRP-2) was obtained.

Example 3 [Blending of Resin Composition (UP-3)] "Polylite FS"
-150 ”in 93 parts,“ DUALITE M6017
AE ”and“ FRANKLIFIBER A-
30 "and" NS-100 "as a general filler
50 parts of [Calcium carbonate manufactured by Nitto Powder Chemical Co., Ltd.] and 10 parts of a styrene monomer were mixed to obtain a target resin composition.

[Spray-up molding] In the same manner as in the spray-up molding of Example 1, 83 parts of the resin composition (UP-3) and about 1 part of glass roving having a length of 12 mm were used.
A desired FRP molded product FRP-3 was obtained from 7 parts and a curing agent in a ratio of 1.0% to the resin composition.

Example 4 [Blending of Resin Composition (UP-4)] "Polylite FS"
The desired resin composition was obtained by mixing 95 parts of "-150" with 5 parts of "Scotchlite Glass Bubbles B46 / 4000" (manufactured by Sumitomo 3M Limited).

[Spray-up molding] In the same manner as in the spray-up molding of Example 1, 85 parts of the resin composition (UP-4) and about 1 part of a glass roving having a length of 12 mm were prepared.
From 5 parts and a curing agent having a ratio of 1.0% to the resin composition, an intended FRP molded product FRP-4 was obtained.

Example 5 [Blending of Resin Composition (UP-5)] "Polylite FS"
"-150" in 99.5 parts, "Expancel 551
DE "(product of Nippon Philite Co., Ltd.) was mixed to obtain the desired resin composition.

[Spray-up molding] In the same manner as in the spray-up molding of Example 1, 77 parts of the resin composition (UP-5) and about 2 parts of a glass roving having a length of 16 mm were used.
An intended FRP molded product (FRP-5) was obtained from 3 parts and a curing agent having a ratio of 1.0% to the resin composition.

Example 6 [Blending of Resin Composition (UP-6)] "Polylite FS"
-150 ”, 80 parts, 5 parts of“ Scotchlight Glass Bubbles B46 / 4000 ”and“ Talc SS ”
15 parts of [star-shaped filler manufactured by Nippon Talc Co., Ltd.] was mixed to obtain a target resin composition.

[Spray-up molding] In the same manner as in the spray-up molding of Example 1, 85 parts of the resin composition (UP-6) and about 15 parts of a glass roving having a length of 6 mm were used.
A desired FRP molded product (FRP-6) was obtained from the parts and the curing agent at a ratio of 1.0% to the resin composition.

Example 7 [Blending of Resin Composition (UP-7)] "Polylite FS"
-150 ”,“ DUALITE M6017 ”
One part of "AE" and 15 parts of "talc SS" were mixed to obtain a target resin composition.

[Spray-up molding] In the same manner as in the spray-up molding of Example 1, 82 parts of the resin composition (UP-7) and about 1 part of a glass roving having a length of 12 mm were used.
An intended FRP molded product (FRP-7) was obtained from 8 parts and a curing agent having a ratio of 1.0% with respect to the resin composition.

Comparative Example 1 [Blending of Resin Composition (UP-A)] "Polylite FS"
−150 ”and 200 mesh“ NS ”
-200 "[calcium carbonate manufactured by Nitto Powder Chemical Co., Ltd.] was mixed with 100 parts by volume to obtain a desired resin composition. The calcium carbonate content of this is 5
It was 1% by weight.

[Spray-up molding] In the same manner as in the spray-up molding of Example 1, 89 parts of the resin composition (UP-A) and about 1 part of a glass roving having a length of 16 mm were used.
An attempt was made to obtain a control FRP molded product (FRP-1) from 1 part and a curing agent at a ratio of 1.0% to the resin composition. A)
However, it could not be applied under normal conditions, and after all, no FRP molded product was obtained.

Comparative Example 2 [Blending of Resin Composition (UP-B)] "Polylite FS"
−150 ”and 200 mesh“ NS ”
By mixing 60 parts by volume of "-200" and 5 parts by volume of a styrene monomer, a resin composition for control was obtained. This had a calcium carbonate content of 37% by weight.

[Spray-up molding] In the same manner as in the spray-up molding of Example 1, 83 parts of the resin composition (UP-B) and about 1 part of a glass roving having a length of 16 mm were used.
An attempt was made to obtain a control FRP molded product (FRP-2) from 7 parts and a curing agent having a ratio of 1.0% with respect to the resin composition, but the thickness of the FRP was about 3 mm. The resin composition and glass fibers on the L-shaped vertical surface slipped off, and as a result, it was not possible to obtain a control FRP molded product.

Comparative Example 3 [Blending of Resin Composition (UP-C)] "Polylite FS"
−150 ”and 200 mesh“ NS ”
"-200" was mixed with 40 parts by volume to obtain a resin composition UP-C for control. Its content of calcium carbonate was 30% by weight.

[Spray-up molding] In the same manner as in the spray-up molding of Example 1, a control resin composition (UP
-C), about 25 parts of a glass roving having a length of 25 mm, and a curing agent having a ratio of 1.0% to the resin composition, a control FRP molded product (FRP-3) was prepared. However, large bubbles were generated, and poor curing occurred. In addition, glass fibers stood on the surface, and high quality F
An RP molded product could not be obtained.

Comparative Example 4 [Blending of Resin Composition (UP-D)] "Polylite FS"
A resin composition for control (UP-D) was prepared using 100 parts by volume of "-150".

[Spray-up molding] In the same manner as in the spray-up molding of Example 1, 80 parts of the resin composition (UP-D) and about 2 parts of the glass roving having a length of 16 mm were used.
An attempt was made to obtain a control FRP molded product (FRP-4) from 0 parts and a curing agent having a ratio of 1.0% with respect to the resin composition, but the thickness of the FRP was about 3.0 mm. Where L
The resin composition and the glass fibers on the vertical surface of the shape slipped off, so that an FRP molded product could not be obtained after all.

Table 1 shows the raw material ratios of the above resin compositions.
Table 2 shows the raw material ratio of the spray-up molding, Table 3 shows the characteristics of the resin composition, and Table 4 shows the evaluation of the spray-up molding.

[0063]

[Table 1] The ratio of each raw material in the table is parts by weight in the examples and parts by volume in the comparative examples.

[0064]

[Table 2] The ratio of each resin composition to the glass fiber in the table is part by weight in the example and is part by volume in the comparative example. The amount of the curing agent used is a ratio to the resin composition.

[0065]

[Table 3] The measurement of viscosity, thixotropic degree and gel time is based on JIS K
-6901, and 55% ME
1.0 part of KPO was added.

[0066]

[Table 4]

[Footnotes in Table 4] Coating characteristics: State of spray pattern of resin by spray gun.

[0068]

According to the present invention, an extremely useful resin composition capable of completely eliminating the impregnation and defoaming operation using a roller or the like in a spray-up molding method,
FRP spray-up molding method, which can be used and applied to FRP for various applications.

Continuation of the front page (51) Int.Cl. ⁷ identification code FI // B29K 101: 10 105: 06 105: 16 (58) Investigated field (Int.Cl. ⁷ , DB name) C08L 1/00-101 / 16 C08K 3/00-13/08 C08J 3/20 B29C 67/14

Claims (3)

(57) [Claims] 1. A thermosetting resin (A), a spherical hollow filler (B), and a star-shaped filler (excluding mica powder ) (C) are combined with a resin (A): a filler (B). ): The weight ratio of the filler (C) is 99.5: 0.5: 0 to 80.0: 5.0: 1.
A resin composition for spray-up molding, which is contained so as to be 5.0. (However, mica powder
Not included) 2. A thermosetting resin (A), a spherical hollow filler (B), and a star-shaped filler (excluding mica powder) (C) as essential components. The resin composition according to (but not containing mica powder), and a fiber reinforcing material,
An FRP spray-up molding method, characterized by applying by using a spray-up machine. And wherein the thermosetting resin (A), the spherical hollow filler and (B), (excluding mica powder) star-like filler (C) and the, you as essential components a resin composition Things (however, my
And not including mosquitoes powder), a fiber reinforcement length 3~25mm ing, by allowed to coating using a spray-up machine, FRP spray-up molding method characterized by obtaining the FRP molded product.