JPH03138146A - Fiber-reinforced thermoplastic resin laminated-body - Google Patents

Abstract

PURPOSE:To improve the surface smoothness and heat-resistant dimensional stability by incorporating a specified thermoplastic resin, a styrenic resin, a styrenic resin with no epoxy group and a thermoplastic resin. CONSTITUTION:A thermoplastic resin A wherein the outer layer agent of the thermoplastic resin has at least one polar group selected from a group consisting of carboxyl, hydroxyl and amino groups, a styrenic resin B contg. epoxy groups, a styrenic resin C contg. no epoxy group and a thermoplastic resin D having molecular compatibility with the styrenic resin C are incorporated. The resin compsn. consists of 5-95wt.% ingredient A, 0.01-50wt.% ingredient B, 0-90wt.% ingredient C and 0-90wt.% ingredient D and contains 5wt.% or more sum of the ingredients C and D. 0-50wt.% filler based on sum of the ingredients A-D consisting of a spherical filler with a particle diameter of 50mum or smaller and a single fiber with a fiber diameter of 20mum and an aspect ratio of 0.5-1,000 are incorporated. It is possible thereby to improve the surface smoothness and heat-resistant dimensional stability.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a fiber-reinforced thermoplastic resin laminate useful as a stampable sheet for exterior parts of automobiles, housings of various devices, etc. The present invention relates to a fiber-reinforced thermoplastic resin laminate that can be molded into a molded product that has excellent heat-resistant dimensional stability, 9 surface smoothness, and mechanical strength.

(Conventional technology) Conventional stampable sheets are made of polypropylene.

It is a sheet-shaped molding material made by impregnating glass fiber with a melted thermoplastic resin such as high-density polyethylene, nylon, or polyethylene terephthalate. A molded article is obtained by heating this sheet in a preheating furnace to a temperature higher than the melting point of the material, and then transferring the sheet into a mold and pressing it.

However, conventional stampable sheets.

Because thermoplastic resin is used as a matrix, polymers such as polypropylene and nylon tend to shrink during molding, causing problems such as reinforcing fibers protruding to the surface, impairing surface smoothness, and low heat resistance. be. Various attempts have been made to improve the surface smoothness of stampable sheets. For example, a method of laminating a layer containing relatively short glass fibers or granular fillers on the surface layer of a thermoplastic resin sheet (Japanese Patent Laid-Open No. 524
0588), a method of dispersing short fibers in a thermoplastic resin layer reinforced with long fiber strands (Japanese Patent Publication No. 54-3
6173) and a method of reducing the diameter of glass fibers used in reinforcing mats (Japanese Patent Application Laid-open No. 168731/1983). However, the surface smoothness of molded articles made from sheets obtained by these methods is not sufficient. Furthermore, a method of using a thermoplastic resin and a thermosetting resin in combination (Japanese Unexamined Patent Publication No. 30264/1983).

A method (Japanese Unexamined Patent Publication No. 57-201650) has also been disclosed in which the upper and lower surfaces of a thermoplastic stampable sheet are sandwiched between thin metal plates and then cured. However, these methods
Even if a molded article with good surface smoothness can be obtained, the productivity is poor and the cost is high, making it impractical. As described above, even with the methods proposed in the past, problems such as embossment of reinforcing material fibers on the surface, fine racks, warping, etc. on the surface have not been solved, and this is particularly true in fields where a good appearance is required. It cannot be used as a stampable sheet for molded products.

(Problem to be solved by the invention) The main cause of the decrease in surface smoothness is thought to be shrinkage due to crystallization of the matrix resin during molding and heat shrinkage. It is possible to use it. However, ordinary non-grade polymers have low heat resistance and are difficult to be applied to stampable sheets that require heat resistance such as outer panels for automobiles. Polyphenylene ether resin is an example of a thermoplastic resin that is non-porous and has heat resistance. Polyphenylene ether resin has excellent mechanical properties, electrical properties, heat resistance, and excellent dimensional stability, making it an excellent choice for engineering plastics. It is used for many purposes as.

It has major drawbacks of poor moldability, impact strength, and chemical resistance. In order to obtain a stampable sheet with excellent surface smoothness, a method of blending polyphenylene ether and thermoplastic polyester resin may be considered. For example, Japanese Patent Publication No. 51-21664 proposes an attempt to melt and mix both. However, the resulting compositions exhibit typical incompatible properties because the properties (expressed by sp value, etc.) derived from the molecular structures of the two are significantly different. That is, the mechanical properties of 9 are significantly lower than expected based on both values, and the appearance of molded articles obtained from this composition is also worse than that of the single composition.

On the other hand, Japanese Patent Publication No. 45-997 proposes blending a polyamide resin with the purpose of improving the fluidity of polyphenylene ether.

Polyphenylene ether and polyamide have extremely poor compatibility, and the resulting resin composition has significant deterioration in mechanical properties, and no characteristic properties other than improved fluidity have been obtained.

The present invention has been made to solve the above-mentioned conventional drawbacks, and its purpose is to provide a fiber-reinforced thermoplastic resin laminate from which a molded product with excellent surface smoothness and heat-resistant dimensional stability can be obtained. be.

(Means for Solving the Problems) The present invention improves the drawbacks of each resin without reducing the excellent properties of each resin by blending thermoplastic resins with different properties and poor compatibility. This was done based on the knowledge that a thermoplastic resin laminate with excellent smoothness and heat-resistant dimensional stability can be obtained.

In other words, the fiber-reinforced thermoplastic resin laminate of the present invention is a fiber-reinforced thermoplastic resin laminate in which a sheet-like core material made of a fibrous reinforcing material and a thermoplastic resin, and a thermoplastic resin outer layer material are laminated and integrated. And.

A thermoplastic resin (A) in which the thermoplastic resin outer layer material has at least one polar group selected from the group consisting of a carboxyl group, a hydroxyl group, and an amino group and has a melting point of 150°C to 300°C, an epoxy group Styrenic resin containing (
B), 5 to 95% by weight of component (A), containing a styrenic resin (C) not containing an epoxy group and/or a thermoplastic resin (D) having molecular compatibility with the styrene resin (C); 0.01% by weight or more and less than 50% by weight of component (B),
0 to 90% by weight of component (C) and 0 to 9% of component (D)
Contains at a ratio of 0% by weight, and contains component (C) and component (D)
The thermoplastic resin outer layer material contains components (A) and (B) in a total of 5% by weight or more.
, Contains 0 to 50% by weight of filler based on the total amount of (C) and (D), and the filler is a spherical filler (α) with a particle size of 50 μm or less and/or a fiber diameter of 20 μm or less, and Single fiber (β
), thereby achieving the above objective.

The fibrous reinforcing material used in the sheet-like core material includes continuous fibers and short fibers. Continuous fibers include continuous strand pine troping cloth, glass cloth, etc., and short fibers include chopped strand mats, 21 dollar mats, surfacing mats, glass paper, etc., and lamimats, etc., which use these in combination can also be used. . Glass fibers are preferably used as the fibers constituting the core material, and if necessary, inorganic fibers or organic fibers such as carbon fibers and aramid fibers are used. It is preferable that the glass fiber is contained in an amount of 50% by weight or more, but if it is less than 50% by weight, the physical properties of the sheet-like core material will deteriorate and the cost will increase because a large amount of other fibers will be contained. The length of the fibers used in the fibrous reinforcing material of the present invention is preferably 5 mm or more, more preferably 10 mm or more. If the length of the fiber is shorter than 5 mm, the reinforcing effect will be insufficient.

When the above fibrous reinforcing material is made of glass mat etc.
It is preferable that the coarse and dense rings be as small as possible.

For example, as a method for evaluating the degree of dense and dense rings.

There is a method shown in FIG. In FIG. 1, 1 is a camera, 4 is a light source, 3 is a sample made of a fibrous reinforcing material, and 2 is transmitted light. Place sample 3 at a predetermined position on the device,
The brightness of the transmitted light 2 when the light from the light source 4 passes through the sample 3 and reaches the camera 1 is measured. As shown in Fig. 2, the brightness of the transmitted light received by the camera 1 is as follows:
Pixel unit: 1 mm, 512x512=262144
Image processing is performed using (pcs)).

As shown in FIG. 3, the variation in brightness of the processed transmitted light is plotted into a histogram, the relative standard deviation (CV%) is determined, and the degree of the ring of density is evaluated. The Cv% of the fibrous reinforcing material such as the mat is preferably 20% or less, more preferably 15% or less. If it is larger than 20%, the reinforcing effect tends to vary.

A part of the fibrous reinforcing material may be replaced with a commercially available surface material, such as a surfacing mat, a needle mat, a cloth made of natural fibers, a knitted nonwoven fabric, or paper.

The thermoplastic resin used for the sheet-like core material is as follows:
Known polyethylene terephthalate (PET).

An example is polybutylene terephthalate (PBT).

The thermoplastic resin may be a homopolymer, a modified polymer graft copolymer, etc., or may be an appropriate blend or alloy of multiple types of the above resins. The following additives can be added and blended with the above thermoplastic resin. Examples of additives include wollastonite, mica, calcium carbonate, calcined clay, glass peas, glass flakes, glass balloons, and shirasu balloons.

Inorganic fillers such as ceramic balloons; Crystal nucleating agents such as talc, titanium oxide, and carbon black; Polyoxyalkylene compounds, polyhydric alcohol derivatives, higher fatty acid esters, higher fatty acid metal salts, polyvalent carboxylic acid esters, and high molecular weight fats. Examples include crystallization accelerators such as group polycarboxylic acid salts and polyhydric alcohol esters. Usually 5 for thermoplastics.

The amount of the inorganic filler added is preferably up to about 70% by volume, the amount of the crystal nucleating agent is up to about 50% by weight, and the amount of the crystallization promoter is up to about 10% by weight. Furthermore, an antioxidant and an ultraviolet absorber are added to the thermoplastic resin as necessary.

Stabilizers such as hydrolysis resistance improvers, plasticizers, lubricants, flame retardants, flame retardant aids, antistatic agents, 2 coloring agents, conductivity imparting agents,
Sliding properties improvers (solid lubricants, liquid lubricants), multifunctional crosslinking agents, impact resistance improvers (e.g. glass transition temperature (hereinafter referred to as Tg) below 0°C, preferably below -20°C) rubber-like substances, more preferably reactive group-containing rubbers),
Inorganic fillers and fibrous reinforcements other than those listed above (e.g., glass fibers).

Carbon fiber, graphite fiber, silicon carbide fiber.

silicon nitride fibers, arsenic nitride fibers, potassium titanate whiskers, heat-resistant organic fibers), conductivity imparting agents (for example, metal fibers, polyacetylene fibers, metal powders).

Additives such as iron phosphate, organic conductive polymers, etc.) can also be blended. When blending inorganic fillers and inorganic fibers, use silane coupling agents, titanate coupling agents,
A zircoaluminum coupling agent or the like may be added.

The content of the fibrous reinforcing material relative to the thermoplastic resin in the sheet-like core material is preferably 10 to 70% by weight, more preferably 20 to 60% by weight. If the content of the reinforcing material is less than 10% by weight, the reinforcing effect will be poor, and if it is more than 70% by weight, fluidity will be lacking and moldability will be impaired.

The thermoplastic resin outer layer material used in the present invention has a small number of polar groups (one type selected from the group consisting of carboxyl groups, hydroxyl groups, and amino groups, and has a melting point of 150 to 30
Thermoplastic resin (A) at 0°C (hereinafter referred to as component (A));
Styrenic resin (B) containing an epoxy group (hereinafter referred to as component (B)); Styrenic resin (C) not containing an epoxy group (hereinafter referred to as component (C)); and/or the above styrenic resin Thermoplastic resin (D) having molecular compatibility with resin (C) (hereinafter referred to as "thermoplastic resin").

This is a thermoplastic resin composition containing component (D). Each component will be explained below.

Examples of the component (A) include polyethylene terephthalate and polypropylene terephthalate.

Polybutylene terephthalate, polycyclohexane dimethylene terephthalate polyoxyethoxybenzoate, polyethylene naphthalate, the above polyethylene components and other acid components and/or glycol components (e.g., isophthalic acid, p-oxybenzoic acid, adipic acid, sebacic acid, geltal) acid, diphenylmethanedicarboxylic acid, acid components such as dimer acid; hexamethylene glycol, diethylene glycol, neopentyl glycol,
polyesters copolymerized with glycol components such as bisphenol A and neopentyl glycol alkylene oxide adducts, aromatic polyester/polyether block copolymers, and aromatic polyester/polylactone block copolymers.

Broadly defined polyester such as polyarylate; nylon 6,
Nylon 616. Nylon 6.9. Nylon 6110,
Nylon 6, 12. Nylon 6/6,6, polyxylylene adipamide, polyhexamethylene terephthalamide,
Examples include polyamides such as polyphenylene phthalamide, polyxylylene adipamide/hexamethylene adipamide, polyester amide elastomer, polyether amide elastomer, polyether ester amide elastomer, and dimer acid copolymerized polyamide. The resin used may be a single resin, a blend of multiple resins, or a copolymer thereof. The melting point of the above resin is 200℃ ~
300°C is preferred. Usually, the above-mentioned polyester resin preferably has an intrinsic viscosity of 0.4 or more, particularly 0.5 or more, as measured at 30"C in a mixed solvent of phenol/tetrachloroethane (674 weight ratio). Preferably. The above polyamide usually has a relative viscosity (JIS K
6810-1977) is preferably 1.8 or more, particularly preferably 2.0 or more.

The above component (B) is a styrene-containing polymer such as polystyrene copolymerized or graft copolymerized with an epoxy group-containing copolymerizable unsaturated monomer, an acrylonitrile-styrene copolymer, and a styrene-butadiene copolymer. is exemplified. Examples of the epoxy group-containing copolymerizable unsaturated monomer include glycidyl methacrylate and glycidyl acrylate.

Vinyl glycidyl ether, allyl glycidyl ether, glycidyl ether of hydroxyalkyl (meth)acrylate, glycidyl ether of polyalkylene glycol (meth)acrylate.

An example is glycidyl itaconate. The content of the above-mentioned epoxy group-containing copolymerizable unsaturated monomer is usually 0.1 to 30% by weight, preferably 0.5 to 30% by weight, based on component (B).
It is 20% by weight.

The above component (C) includes homopolymers such as polystyrene, polychlorostyrene, and polyα-methylstyrene;
Styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile copolymer, styrene-acrylonitrile-acrylate copolymer, styrene-acrylonitrile-butadiene copolymer, styrene-butadiene rubber modified polystyrene, EPDM rubber Examples include polystyrene thermoplastic elastomers such as modified polystyrene, acrylic rubber modified styrene/acrylonitrile copolymer, styrene/maleic acid copolymer, and hydrogenated styrene/butadiene block copolymer.

The component (D) is a resin that has molecular compatibility with the component (C) (a blend that is compatible on the molecular order, changes the Tg of the component (C), and provides a single Tg). The component (D) is a polyphenylene ether resin whose main constituent unit is a repeating unit represented by the following general formula (1).

(In the formula, + RI + RZ + R3 and R4 are independently hydrogen.

It is a halogen, a hydrocarbon group, a substituted hydrocarbon group, a cyano group, an alkoxy group, a phenoxy group, or a nitro group, and n indicates the degree of polymerization. ) Specific examples of R,, R2, R1 and R4 include hydrogen, chlorine, bromine, iodine, methyl, ethyl, propyl,
Allyl, phenyl, benzyl, methylbenzyl, chloromethyl, bromomethyl, cyanoethyl, cyano, methoxy, ethoxy, phenoxy.

Examples include groups such as nitro. Examples include:

Poly-2,6-dimethyl-1,4-phenylene ether.

Poly-2,6-danityl-1,4-phenylene ether.

Poly-2,6-diprobyl-1,4-phenylene ether.

Poly-2,6-simethoxy 1,4-phenylene ether Poly-2,6-cyclomethyl-1,4-phenylene ether, Poly-2,6-dipromemethyl-1,4-phenylene ether, Poly-2,6-diphenyl-1 ,4
-phenylene ether, poly-2,6-dyryl-1.
4-phenylene ether, poly-2,6-dichloro-1
, 4-phenylene ether, poly-2,5-dimethyl-
Examples include 1,4-phenylene ether, poly-2,6-dipendylene 1,4-phenylene ether, and the like.

A preferred polyphenylene ether resin is a polymer in which R2 and R4 in the general formula have an alkyl group, particularly an alkyl group having 1 to 4 carbon atoms, and n is preferably 50 or more.

The above component (C) and component (D) may be obtained by polymerizing one of the components in the presence of the other component.

By promoting the reactivity between the epoxy group of component (B) and component (A), or by opening the ring of the epoxy group, component (
It is preferred to use a catalyst to improve the affinity with A). Although the reaction between component (A) and the epoxy group is effective even without a catalyst, the reaction is significantly accelerated when a catalyst is used. Catalysts are generally amines, phosphorus compounds, monocarboxylic acids and/or dicarboxylic acids having 10 or more carbon atoms, 1-a or II of the Periodic Table of the Elements.
- It is preferable to mix group a metal salts and the like. Particularly preferred are trivalent phosphorus compounds such as tributylphosphine and triphenylphosphine, and metal salts of stearic acid such as calcium stearate and sodium stearate. These catalysts may be used alone or in combination of two or more. Moreover, the effect remains the same whether the above catalyst is added all at once or divided into parts. The amount to be blended is not particularly limited, but it is usually 3 parts by weight or less, preferably 0.03 to 2 parts by weight, per 100 parts by weight of component (A).

Component (A) contained in the thermoplastic resin outer layer material.

The blending ratio of (B), (C) and (D) is as follows:
A) is 5 to 95% by weight, component (B) is 0.01% to less than 50% by weight, component (C) is 0 to 90% by weight, and component (D) is 0 to 90% by weight, The total amount of component (C) and component (D) is 5% by weight or more, and these can be changed as appropriate depending on desired physical properties, cost, etc. If component (A) is too small, heat resistance (baking paintability),
Chemical resistance decreases, and adhesion to the sheet-like core material decreases. If component (B) is too small, component (8) and component (C)
and/or the compatibility with (D) decreases, resulting in a decrease in physical properties such as mechanical strength.

Components (B) and (C) contained in the thermoplastic resin outer layer material
The Tg of the mixture (E) consisting of and (D) is the mold temperature (hereinafter referred to as
It is preferable that the temperature range is from MT to MT + 50°C. If 7g force < lower than MT, the mixture (
Since E) has fluidity even after molding, the reinforcing material is embossed on the surface of the molded product due to the heat shrinkage of the component (A).

The surface appearance deteriorates. If the temperature is higher than 7 g force < MT + 50°C, the melt viscosity of the mixture (E) during molding becomes high, which impairs moldability. Furthermore, the adhesion to the core material deteriorates, resulting in peeling and the like.

It is preferable that the thermoplastic resin outer layer material further contains a spherical filler (α) and/or a single fiber (β). This is used to prevent the fibrous reinforcing material in the sheet-like core material from rising to the surface.

The particle size of the spherical filler (α) is preferably 50 μm or less.

More preferably, it is 30 μm or less. If the particle size is larger than 50 μm, the fibers of the core material can be prevented from being exposed to the surface, but unevenness due to the filler becomes large.

The fiber diameter of the single fiber (β) is preferably 20 μm or less,
More preferably it is 10 um or less. The aspect ratio of the single fiber (β) is preferably 0.5 to 1.000.

(
The larger the amount of these fillers added, the smaller the aspect ratio of single fibers (β) is preferably selected.

Mixing ratio (α/β) of the above spherical filler (α) and single fiber (β)
) is preferably 10/90 to 90/10, more preferably 20/80 to 80/20 by weight. Spherical filler (
If the ratio of α) is too low, long-period spots in the resulting laminate will become large, and conversely, if the ratio of single fibers (β) is too low, short-period spots will become large.

The addition amount of the filler consisting of the spherical filler (α) and the single fiber (β) is the component (A) contained in the thermoplastic resin outer layer material.
), (B), (C) and (D), preferably 0 to 50% by weight, more preferably 1 to 4% by weight.
It is 0% by weight. If the amount added exceeds 50% by weight, the impact resistance of the molded product will decrease and the adhesion to the sheet-like core material will be impaired.

The thermoplastic resin outer layer material may contain components other than those mentioned above depending on the intended use. For that.

Examples include crystal nucleating agents and crystallization promoters such as talc, mica, titanium oxide, and carbon black. When component (8) is an ethylene terephthalate polyester, the crystallization promoter may be a polyoxyalkylene compound compatible with the polyester, a polyhydric alcohol derivative, a higher fatty acid ester, a higher fatty acid metal salt, or a polycarboxylic acid. Acid ester, high molecular weight aliphatic polycarboxylate.

Polyhydric alcohol esters and the like are used. usually.

The amount of the crystal nucleating agent added is preferably up to about 50% by weight, and the amount of the crystallization promoter is up to about 10% by weight, based on the composition of the thermoplastic resin outer layer material. Plus, antioxidants.

UV absorbers, stabilizers such as hydrolysis resistance modifiers, plasticizers, lubricants, flame retardants, flame retardant aids, antistatic agents, 9 colorants,
Conductivity imparting agent, sliding property improver (solid lubricant, liquid lubricant), multifunctional crosslinking agent, impact resistance improver (for example, a rubber-like substance with a Tg of 0°C or lower, preferably -20°C or lower) , more preferably a reactive group-containing rubber), an inorganic filler other than the above,! Li fibrous elastic reinforcement materials, such as glass fibers, carbon fibers, graphite fibers, silicon carbide fibers, silicon nitride fibers, arsenic nitride fibers, potassium titanate whiskers, heat-resistant organic fibers, conductivity imparting agents (for example, metal fibers) , polyacetylene fibers, metal powder, iron phosphate, carbon black, organic conductive polymers, etc.).

When blending the above-mentioned filler, inorganic filler, and inorganic fiber into the thermoplastic resin outer layer material, a silane coupling agent, a titanate coupling agent, a zircoaluminum coupling agent, etc. may be used in combination.

Other resins can also be blended with the thermoplastic resin outer layer material to the extent that the object of the present invention is not impaired.

The method for producing the thermoplastic resin composition constituting the thermoplastic resin outer layer material used in the present invention is not particularly limited, and any conventional known method may be employed. For example, there are melt-kneading methods using an extruder, a Banbury mixer, a roll, a kneader, and the like. Further, the kneading may be performed in multiple stages. For example, after kneading components (A) and (B), other components may be kneaded. The obtained resin composition is made into a film using a film manufacturing method such as a T-die method to obtain a film-like thermoplastic resin outer layer material.

To produce the sheet-like core material used in the present invention, the composition constituting the thermoplastic resin described above is melt-kneaded and pelletized by a known method, and then formed into a film using an extrusion device such as a T-die. do. A predetermined number of sheets of the obtained film-like thermoplastic resin and the above-mentioned fibrous reinforcing material are alternately stacked,
The obtained laminate is placed in a mold and heated. After the film-like resin in the laminate is completely melted, the pressure is increased to impregnate the fibrous reinforcing material with the molten resin. Thereafter, a sheet-like core material is obtained by cooling.

Furthermore, a sheet-like core material can also be obtained continuously using a known double steel belt press or the like.

The fiber-reinforced thermoplastic resin laminate of the present invention is obtained by laminating the above-mentioned film-like thermoplastic resin outer layer material on the upper and lower surfaces of the above-mentioned sheet-like core material, heating to melt the outer layer material, and then cooling-pressing. It will be done.

The fiber-reinforced thermoplastic resin laminate of the present invention can be used as a stampable sheet for various applications such as exterior parts for automobiles and housings for various devices.

(Example) The present invention will be explained below based on examples.

Note that the percentages in the examples are based on weight.

Creation of outer layer material of thermoplastic resin> Backyard ■1 Polyethylene terephthalate (intrinsic viscosity [η] 0.63
．． 45% (measured at 30°C in phenol/tetrachloroethane mixed solution (674 weight ratio)), 5% epoxy group-containing styrene resin (styrene copolymer copolymerized with 10 mol% glycidyl methacrylate), no epoxy group Styrenic resin (high impact polystyrene) 5%,
and 45% poly-2,6-dimethyl-1,4-phenylene ether (Fi limiting viscosity (η) 0.58) powder were mixed in a blender.The resulting resin mixture was
Axial extruder (Ikegu Iron Works Co., Ltd.)

PC) 1-30), cylinder temperature 280℃
The mixture was kneaded and extruded into pellets. The obtained pellet was dried in a vacuum dryer at 120° C. for 5 hours, and then molded in an injection molding machine (Metsuki Jushi Kogyo Co., Ltd., model FS-75) to obtain a thermoplastic resin outer layer material. The cylinder temperature at this time was 280°C. Moreover, the mold temperature was 7Q'C.

The heat deformation temperature and bending strength of the obtained outer layer material were measured.
The surface properties were evaluated. The results are shown in Table 1. In addition, each test method is as follows.

(1) Heat distortion temperature According to ASTM D-648, length 126 mm, medium 1
2, 18.6 kg on a 6 mm thick 6.3 mm test piece
The test piece was heated at a rate of 2°C per minute while a bending stress of /c was applied, and the temperature when the amount of deflection reached 0.254111111 was determined.

(2) Bending strength Measured according to ASTM D-790.

(3) Surface properties The molded product was visually evaluated for sink marks, surface gloss, etc.

(Q indicates that the evaluation result is good, and × indicates that the evaluation result is poor.) 1-2 to 1-12 and 1-1 to 1-6 Example 1-1 with the resin composition shown in Table 1 An outer layer material was obtained by the same process as above. The heat deformation temperature and bending strength of the obtained outer layer material were measured in the same manner as in Example 1-1, and the surface characteristics were evaluated.

The results are shown in Table 1.

(The following is a blank space) From the results of Table 1, 1) the resin composition for the thermoplastic resin outer layer material of the present invention contains a styrene resin containing an epoxy group; 2) it has good surface properties and excellent bending strength; It was confirmed that an outer layer material could be obtained. Also, in the above,
It was also observed that the heat distortion temperature of polyphenylene oxide (poly-2,6-dimethyl-1,4-phenylene ether) was improved and the chemical resistance was improved.

Preparation of sheet-like core material> Polyethylene terephthalate (intrinsic viscosity [η] 0.63
) and glass beads (manufactured by Toshiba Ballotini, EGB-7)
31B) was mixed at a ratio of 30% by volume. This mixture was supplied to a 30 m 1φ twin-screw extruder (described above) and pelletized at a cylinder temperature of 275°C. After drying the obtained pellet at 140° C. for 5 hours in a hot air dryer.

A sheet with a thickness of about 500 μm was obtained from this pellet using a 40-dish φ extruder (manufactured by Aji Nippon Steel Works).

The obtained sheet and glass mat (MC-45 manufactured by Nittobo Co., Ltd.)
OA or Nippon Electric Glass ■ improved man), CV% is Table 4
) were cut into 190 mm x 190 mm each, and 4 sheets of glass mat (fabric weight 450 g/M") were stacked alternately with the sheet, and sandwiched between two molds set to a thickness of 3 mm.
It was preheated at 95° C. for about 2 minutes without any load. After the sheet-shaped resin was completely melted, the pressure was gradually increased to sufficiently impregnate the molten resin into the glass mat core material. After that, immediately throw it into water to cool it down, and then
mm×2 cylinder) was obtained.

Preparation of film-like thermoplastic resin outer layer material> The components shown in Table 4 were blended in the same manner as in Example 1-1. The obtained resin composition was supplied to a 30-bar φ twin-screw extruder (described above),
It was pelletized at a cylinder temperature of 290°C. The obtained pellet was molded into a film with a thickness of 300 μm at 280° C. using a 40 mmφ extruder (described above) to obtain a film-like thermoplastic resin outer layer material. This is 190mm x 19
It was cut to 0 mm.

Preparation of fiber-reinforced thermoplastic resin laminate> The above film-like outer layer material was layered on one side of the above-mentioned sheet-like core material (cut to 190 mm x 190 mm).

The resin was completely melted in an infrared furnace. Next, it was put into a mold kept at room temperature (25° C.) and cooled by pressing. At this time, the press pressure was 30 kg/Cl1a in terms of resin pressure.
It was set to Next, a film-like outer layer material was placed on the other surface of the sheet core material, and the same operation as above was performed to obtain a fiber-reinforced thermoplastic resin laminate.

<Stamping molding> The obtained laminate was cut into 95 au x 95 mm, and both sides were heated in an infrared heating furnace to sufficiently melt the resin.
A flat plate mold (100 mm x 1
00 mm x 3 mm) and immediately press-molded.

A flat plate molded product with dimensions of 100 an x 100 mm x 3 recesses was obtained. Press pressure is resin pressure 150 kg/cIi
It was set to 1.

The surface smoothness of the obtained molded product and the adhesion between the outer layer material and the core material were evaluated. Each evaluation method is shown below. The results are shown in Table 4.

(4) Surface smoothness: Performed in accordance with surface roughness standard JIS B 0601-1982.

The surface roughness of the flat plate molded product was measured using a surface roughness profile measuring machine (Surfcom 300 B, manufactured by Tokyo Seimitsu ■).

The surface roughness was represented by the center line average roughness Ra. It was measured with a cant-off value of 2.5M, and the result was Ra(2,,
5). Ra is expressed by the following formula.

The roughness was evaluated by relative comparison with the roughness of a face milling plate of a comparison roughness standard piece manufactured by Metrol Aji Co., Ltd., Model 5S-03-2, and was determined as follows.

(5) Adhesion The adhesion between the outer layer material and the core material was determined by a substrate test according to JIS K 5400, and the relative comparison with the evaluation score was shown in Table 4.
The relationship between the middle evaluation and the evaluation score of the foundation examination is as follows.

Table 3 As shown in Table 4, a sheet-like core material was obtained by appropriately changing the Cv% of the glass mat, and a film-like thermoplastic resin outer layer material was obtained using a resin having the composition shown in Table 4. Furthermore, the molding was performed in the same manner as in Example 2-1, except that the molding was performed at the molding temperature shown in Table 4.

A molded product was obtained. The surface smoothness and adhesion of the obtained molded article were evaluated in the same manner as in Example 2-1.

The results are shown in Table 4.

(The following is a blank space) From the results in Table 4, it was confirmed that the fiber-reinforced thermoplastic resin laminate of the present invention yields a molded article with excellent surface smoothness and adhesion.

(Effects of the Invention) According to the present invention, excellent surface smoothness and heat-resistant dimensional stability are achieved without deteriorating the excellent properties of each resin contained in the thermoplastic resin outer layer material.

Moreover, it is possible to provide a fiber-reinforced thermoplastic resin laminate that provides a molded product with good adhesion between the outer layer material and the sheet-like core material. The fiber-reinforced thermoplastic resin laminate of the present invention can be suitably used as a stampable sheet for various applications such as exterior parts for automobiles having a good appearance and housings for various types of equipment.

Figure 1 is an explanatory diagram of a device for measuring the degree of unevenness of fibrous reinforcing materials such as mats, Figure 2 is an explanatory diagram of the base grain used for image processing in the camera, FIG. 3 is a histogram showing the luminance of transmitted light on the horizontal axis and the number of base eyes on the vertical axis.

1...Camera, 2...Transmitted light, 3...Sample,
4... Light source, a... Histogram of good fibrous reinforcing material b... Histogram of bad fibrous reinforcing material.

that's all

Claims (1)

[Scope of Claims] 1. A fiber-reinforced thermoplastic resin laminate formed by laminating and integrating a sheet-like core material made of a fibrous reinforcing material and a thermoplastic resin, and a thermoplastic resin outer layer material, which The plastic resin outer layer material contains a thermoplastic resin (A) having at least one polar group selected from the group consisting of a carboxyl group, a hydroxyl group, and an amino group and having a melting point of 150°C to 300°C, and an epoxy group. a styrene resin (B), a styrenic resin (C) that does not contain an epoxy group, and/or a thermoplastic resin (D) that has molecular compatibility with the styrene resin (C).
5 to 95% by weight of component (A), 0.01% to less than 50% by weight of component (B), and 0 to 90% by weight of component (C)
and a resin composition containing component (D) in a proportion of 0 to 90% by weight, and containing component (C) and component (D) in a total of 5% by weight or more, and the thermoplastic resin outer layer material contains 0 to 50% by weight of filler based on the total amount of components (A), (B), (C) and (D), and the filler is a spherical filler (α
) and/or a single fiber (β) having a fiber diameter of 20 μm or less and an aspect ratio of 0.5 to 1,000. A fiber-reinforced thermoplastic resin laminate.