JPH10193350A - Stamping molding material and its manufacture - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve external appearance, strength, elastic modulus and impact strength of a molded product by heating and pressurizing a composite laminate having thermoplastic resin layers laminated via organic peroxide layers on both surfaces of glass fiber paper body containing thermoplastic resin, and molding it in a sheet-like article. SOLUTION: Organic peroxide layers 12a, 12b are provided on both surfaces of glass fiber paper body 11. Further, thermoplastic resin layers 13a, 13b made of thermoplastic resin films are laminated on surfaces of the layers 12a, 12b. The composite laminate has thermoplastic resin thin layers made of thin thermoplastic resin films laminated between the layer 12a and the paper body 11 and between the layer 12b and the paper body 11. Since the thermoplastic resin thin layers are laminated between the organic peroxide layer and the medium, the molded product having excellent external appearance can be obtained by flow molding.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a stamping molding material, a method for producing the same, and a stamping molding sheet. In particular, a stamping molding material which is lightweight, has high strength, a high elastic modulus and excellent impact resistance, and can obtain a molded article having an excellent appearance by stamping molding, a method for producing the stamping molding material, and a stamping molding material therefor The present invention relates to a flow molded product formed by molding, and a sheet for a stamping molded material that can be suitably used as a stamping molded material.

[0002]

2. Description of the Related Art Conventionally, there has been a composite technique of adding a high modulus fiber such as a glass fiber in order to obtain a higher rigidity and strength while taking advantage of the fact that a thermoplastic resin is easily molded. Are known. The composite fiber-reinforced thermoplastic resin is used as a material for various structural members requiring lightness, high rigidity, and high strength. In particular, plate-shaped or sheet-shaped materials (stamping molding materials) suitable for molding large parts are known.
This stamping molding material is usually molded by heating to a temperature equal to or higher than the melting point of the thermoplastic resin as the matrix. As the molding method, for example, flow molding using a press machine is known. The flow molding method is a molding method in which a stamping molding material is heated to a temperature equal to or higher than the melting point of a matrix resin, and then placed on a mold to compress and flow the material to obtain a desired molded product.

[0003] Two methods are known for producing stamping molding materials. One is a method of producing a glass fiber reinforced composite material (stamping molding material) by impregnating a thermoplastic resin into a mat-shaped glass fiber made of continuous fiber (a dry method), for example, Japanese Patent Publication No. 2-51928. There is a method described in.

Further, a chopped strand of glass fiber having an average length of 7 to 50 mm and a thermoplastic resin are dispersed in a dispersion containing a surfactant (dispersion step), and this dispersion is formed on a mesh belt. There is a method of preparing a sheet-like web (papermaking step), and then applying heat and pressure to the web (sheet forming step) to produce a densely solidified stamping molding material (papermaking method). This technique is disclosed in Japanese Patent Publication No. 2-48423, Japanese Patent Application Laid-Open No. 60-158227, and the like.

In this papermaking method, two types of glass fibers are usually used. One is a fiber which is defibrated to almost a single fiber state during the papermaking (hereinafter, referred to as "fibrillable glass fiber"). The defibrated glass fibers are entangled after papermaking to form a web skeleton. The other is a glass fiber bundle (hereinafter, referred to as “glass fiber bundle”) that has been subjected to a sizing treatment with a sizing agent that is insoluble in an aqueous medium used in a papermaking method. This glass fiber bundle
This is to maintain the convergence state in the stamping molding material and the molded article. The glass fiber bundle is added for improving the impact strength (for example, JP-A-5-140335) and improving the fluidity during flow molding.

The stamping molding material manufactured by the dry method or the papermaking method can obtain a molded article having a desired shape by flow molding. In this flow molding, as shown in FIG. 4A, a stamping molding material 41 cut to a predetermined size is heated to a temperature equal to or higher than a melting point of a thermoplastic resin as a matrix and placed on a lower mold 42. And then
As shown in FIG. 4 (B), the upper mold 43 is closed thereon and pressed by a press to form a molded article 44 having a desired shape. In this flow molding, as shown schematically in the plan views of FIGS. 5 and 6, the original shape portion of the stamping molding material 41 placed on the lower mold at the time of molding is referred to as a charged portion 44a, The matrix resin and the glass fiber are heated and pressurized to form the charged portion 44a.
The part formed by flowing and pressurizing around the periphery of the
4b.

In this flow molding, the stamping molding material produced by the dry method has good resin fluidity when molded by a press machine, and also has good surface smoothness and appearance of the molded product obtained. However, at the end of the flowing resin, the glass fiber and the resin are separated, and only the resin flows. Therefore, there is a possibility that a molded product having a portion that is not filled with glass fibers at the end portions, the ribs, the bosses, and the like and that is not reinforced by the glass fibers may be obtained.

On the other hand, in the stamping molding material manufactured by the papermaking method, since the glass fiber is in a chop shape of 7 to 50 mm, the glass fiber and the resin flow without being separated at the time of molding, and the end of the molded product, the rib, There is an advantage that the boss or the like is uniformly filled with the glass fiber and the resin, and a molded product in which each part is sufficiently reinforced by the glass fiber can be obtained.

[0009]

However, a molded article obtained by using a stamping molding material by a papermaking method has a problem that glass fibers, especially glass fiber bundles are exposed on the surface, and the appearance thereof is deteriorated. This problem is considered to be caused by insufficient covering of the glass fiber with the matrix resin. The glass fiber bundle has a strong convergence force, and the impregnation of the thermoplastic resin into the inside of the convergence is insufficient during the sheet forming step and the subsequent flow molding in the papermaking method, so that it is difficult to cover and conceal the glass fiber with the resin. . In particular, when a stamping molding material or a flow molded product is manufactured using a resin colored with an inorganic pigment, an organic pigment, a dye, or the like, a glass fiber bundle near the surface of the molding material or the molded product appears to appear white. I will. The glass fiber bundle which looks white causes a problem as poor appearance.

[0010] Such poor appearance appears in both the charged portion and the flow portion of the molded product. Then, as a method of concealing the emergence of the glass fiber in the charging portion, a method of bonding a resin film to the surface of a stamping molding material is known (Japanese Patent Laid-Open No. 4-223160). However, this method cannot prevent the glass fiber bundles from floating on the surface of the flow part of the molded product. In a normal flow molding, this molding material is heated to a temperature equal to or higher than the melting point of the resin constituting the matrix, and then charged into a mold having a temperature equal to or lower than the melting point of the resin, and is lowered from above and below in the mold. It flows and is shaped. At this time, the portion (charge portion) of the molding material in contact with the mold having a low temperature solidifies early, and the center portion not in contact with the mold is forcibly extruded and flows to the periphery of the charge portion in advance. Therefore, the covering effect by the resin film extends only to the charged portion and the vicinity thereof, and the glass fiber bundle still appears white on the other molded product surfaces and terminal portions.

[0011] In order to solve this problem, a resin film is previously arranged on the surface of a mold during flow molding, and a preheated sheet is caused to flow in the resin film to obtain a molded product in which the entire surface is covered with the resin film. Is also conceivable. However, this method cannot avoid generation of wrinkles and blisters of the film, and has not been established as a method for obtaining a molded article having good appearance.

When a thermoplastic resin having a high fluidity, that is, a high melt flow rate (MFR) is used for the purpose of improving the concealing property of the glass fiber with the thermoplastic resin,
The appearance of the molded article is improved, but the strength properties are reduced. In particular, in a molded article using a stamping molding material by a papermaking method using a glass fiber bundle, there was a problem that the glass fiber bundle still appeared white and appeared.

Accordingly, a first object of the present invention is to provide a stamping molding material capable of molding a molded article having a glass appearance in which glass fiber bundles are hardly noticeable and having excellent strength, elastic modulus and impact strength. It is in.

A second object of the present invention is to provide a manufacturing method capable of obtaining the stamping molding material.

Further, a third object of the present invention is to provide a flow molded article having excellent appearance, which is obtained by molding the stamping molding material.

Still another object of the present invention is to provide a stamping molded material sheet suitable as a sheet material used for producing the stamping molded material.

[0017]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems. As a result, to improve the concealing property of the glass fiber with the resin, it is necessary to (1) increase the fluidity of the resin; (2) Facilitating resin impregnation by weakening the aggregate state of glass fibers (3) It has been found that it is effective to improve the wettability between resin and glass fibers. By doing so, it has been found that only the resin around the glass fiber locally becomes highly fluid, the deterioration of the strength properties of the molded product is suppressed, and the appearance is improved.

Based on the findings of the above (1), (2) and (3) in the stamping molding material, the present inventors have further studied and found that the glass fiber sheet was thermally bonded to the glass fiber sheet through an organic peroxide layer. A structure in which a thermoplastic resin layer is laminated, or a structure in which a thermoplastic resin layer is laminated on a glass fiber paper to which an organic peroxide is added, solves the above-described problems, and provides a molded article with excellent appearance and strength, elastic modulus, The present inventors have found that they are effective as a stamping molding material capable of molding a molded article having impact strength, and have reached the present invention.

That is, the present invention provides, as a first aspect,
A composite laminate having a glass fiber-made article containing a thermoplastic resin and a thermoplastic resin layer laminated on both sides of the glass fiber-made article via an organic peroxide layer is heated and pressed to form a sheet. The present invention provides a stamping molding material obtained by molding a stamping material.

In a second aspect, the present invention provides a glass fiber paper containing a thermoplastic resin and containing an organic peroxide, and a thermoplastic resin layer laminated on both surfaces of the glass fiber paper. The present invention provides a stamping molding material formed by heating and pressing a composite laminate having the following to form a sheet.

The present invention also relates to a method for producing the above stamping molding material, wherein an organic peroxide layer is formed on both surfaces of a glass fiber sheet obtained by forming a dispersion containing a thermoplastic resin and glass fibers. Forming a composite laminate including a thermoplastic resin layer on the organic peroxide layer, and then heating and pressing the composite laminate to form a sheet into a stamping molding material. To provide.

In a first aspect of the present invention, as a first aspect of the method for producing a stamping molding material, an organic peroxide is applied to one surface of a film made of a thermoplastic resin, and then the organic peroxide-coated surface is further applied. A thin film made of a thermoplastic resin is pressure-bonded to form a multi-layer film, and the multi-layer film is formed on both surfaces of a glass fiber sheet obtained by forming a dispersion containing a thermoplastic resin and glass fiber. An object of the present invention is to provide a method for producing a stamping molding material, which comprises a step of forming a composite laminate by laminating through a thin film, and then heating and pressing the composite laminate to form a sheet.

Further, the present invention provides, as a second aspect of the method for producing a stamping molding material, a method of forming a film comprising a thermoplastic resin having one surface coated with an organic peroxide by dispersing the film containing the thermoplastic resin and glass fibers. Stamping having a step of forming a composite laminate by laminating on both sides of a glass fiber molded article obtained by forming a liquid via an organic peroxide and then heating and pressing the composite laminate to form a sheet. A method for producing a molding material is provided.

Further, the present invention provides, as a third aspect of the method for producing a stamping molding material, an organic resin on both surfaces of a glass fiber sheet obtained by forming a dispersion containing a thermoplastic resin and glass fibers. Forming an oxide layer, then forming a thermoplastic resin layer on the organic peroxide layer to form a composite laminate, and then heating and pressing the composite laminate to form a sheet. It is intended to provide a method for producing a stamping molding material having the following.

In a fourth aspect of the present invention, there is provided a method for producing a stamping molding material, wherein an organic peroxide is added to a glass fiber sheet obtained by forming a dispersion containing a thermoplastic resin and glass fiber. After being contained, a thermoplastic resin layer is formed on both sides of the glass fiber sheet to form a composite laminate, and then the composite laminate is heated and pressed to form a sheet-like stamping material. It is intended to provide a manufacturing method.

The present invention also provides a sheet for a stamping molding material having an organic peroxide layer on one surface of a thermoplastic resin sheet as a base sheet used for the stamping molding material.

Furthermore, the present invention provides a flow molded product obtained by subjecting the stamping molding material to flow molding.

Hereinafter, the stamping molding material of the present invention (hereinafter, referred to as the “molding material of the present invention”), its production method, and the sheet for stamping molding will be described in detail.

The molding material of the present invention has a structure in which an organic peroxide layer and a thermoplastic resin layer are provided on both sides of a glass fiber paper or a thermoplastic resin layer is provided on both sides of a glass fiber paper containing an organic peroxide. The structure to have is an essential form.

The glass fiber sheet as the base material of the molding material of the present invention has a structure in which glass fibers and glass fiber bundles are dispersed in a matrix mainly composed of a thermoplastic resin.

The thermoplastic resin used as the matrix of the glass fiber papermaking material is not particularly limited as long as it is a resin that can be melted by heating. For example, polypropylene, polyethylene, polyolefin resins such as propylene-ethylene copolymer, polybutylene terephthalate,
Polyester resin such as polyethylene terephthalate,
Examples thereof include polycarbonate resins, polyamide resins such as nylon 6 and nylon 66, and acrylonitrile styrene resins, and modified products thereof.
Examples of the modified product include those modified with an unsaturated carboxylic acid such as maleic acid, maleic anhydride, and acrylic acid, or modified with an epoxy group, a hydroxyl group, or the like. Specific examples of the modified product include maleic acid-modified polypropylene, maleic anhydride polypropylene, and acrylic acid-modified polypropylene. In the present invention, the thermoplastic resins may be used alone or in combination of two or more. For example, a mixture of polypropylene and a propylene-ethylene copolymer may be used. Among them, polypropylene and / or a modified product thereof are most preferable because a stamping molding material is flow-molded to obtain a flow-molded article having excellent strength properties and can be obtained at low cost.

In the present invention, it is desirable that the thermoplastic resin used for forming the matrix in the production of the glass fiber sheet is in the form of powder, pulverized product, pellet or the like. Among them, powdery ones are particularly preferable from the viewpoint of uniform dispersibility of the thermoplastic resin.

If necessary, additives such as an antioxidant, an ultraviolet absorber, an ultraviolet stabilizer and a filler may be added to the thermoplastic resin. As an antioxidant, for example,
2,6-di-tert-butyl-4-methylphenol, tetrakis- [methylene-3- (3 ′, 5′-di-
tert-butyl-4′-hydroxy-phenyl) propionate methane, pentaerythyl-tetrakis [3
-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,
5-di-tert-butyl-4-hydroxyphenyl)
Examples include phenolic antioxidants such as propionate and phosphorus-based antioxidants such as tris (2,4-di-tert-butylphenyl) phosphite.

As the ultraviolet absorber, for example, 2- [2
-Hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (3
-Tert-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5
-Di-tert-butyl-2-hydroxyphenyl)-
5-chlorobenzotriazole and the like.

Examples of the UV stabilizer include dimethyl-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine succinate polycondensate. As the filler, for example, talc,
Calcium carbonate, mica, clay, wollastonite,
Examples include alumina, silica, carbon black, and titanium oxide.

In the present invention, two types of glass fibers used in combination with the thermoplastic resin, ie, defibrated glass fibers and glass fiber bundles, are used in the production of the glass fiber papermaking product. The defibrated glass fiber is one in which each fiber is defibrated to almost a single fiber state during papermaking. Further, the glass fiber bundle has a sizing agent that is insoluble in the aqueous medium used in the papermaking method, and is a bundle of a plurality of single fibers.

The glass fibers (defibrillated glass fibers and glass fiber bundles) used in the present invention exhibit a sufficient reinforcing effect and can be obtained as a stamping molding material and a molded article having excellent fluidity during flow molding. From the viewpoint, it is desirable to use a single fiber having an average length of preferably 5 to 50 mm, particularly preferably an average length of 10 to 30 mm. If a glass fiber made of a single fiber having a short average length (defibrillated glass fiber and glass fiber bundle) is used, a sufficient reinforcing effect cannot be obtained. descend. The fiber diameter of the glass fiber is
From the viewpoint of exhibiting a sufficient reinforcing effect, preferably 5 to 30
μm, particularly preferably 8 to 26 μm.

The defibrated glass fiber used in the present invention has been subjected to a surface treatment with a surface treatment agent such as a coupling agent, a sizing agent, and a surfactant. These surface treatment agents are used alone or in combination of two or more. Further, a lubricant, an antioxidant, an antistatic agent, or other additives may be used.

As the coupling agent, for example, vinyl tris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, methacrylate chromic chloride Methoxysilane, γ-aminopropyltriethoxysilane hydrochloride and the like.

Examples of the sizing agent include polyethylene oxides, polyvinyl alcohols, and polyvinyl acetates.

Examples of the surfactant include nonionic surfactants and cationic surfactants. Specific examples include polyoxyethylene alkyl ether, polyoxyethylene alkylphenol, fatty acid sorbitan ester, and alkyl tertiary surfactant. Examples include quaternary ammonium salts, alkylamine salts, and alkylimidazoline derivatives.

The glass fiber bundle used in the present invention preferably has a single fiber count of 25 to 300 fibers / bundle. When the glass fiber bundle of less than 25 fibers / bundle is used, the flowability of the obtained stamping molding material during flow molding does not improve. If the number exceeds 300, a molded product having sufficient mechanical strength (bending, tensile, Izod impact strength, etc.) cannot be obtained by flow molding.

The glass fiber bundle used in the present invention has been surface-treated with a surface treating agent such as a coupling agent, a sizing agent, a surfactant and the like. As the coupling agent and the surfactant to be used, the same ones as those exemplified above as the surface treatment agents used for the surface treatment of the defibrated glass fiber can be used. However, as the sizing agent, it is necessary to use a sizing agent that is insoluble in an aqueous medium used when producing a glass fiber sheet by a papermaking method. As the sizing agent, for example, known ones such as commonly used epoxy type, melamine type, urethane type, polyolefin type, polystyrene type, and allyl resin emulsion are used. Examples of the epoxy emulsion include bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolak resin glycidyl ether, aliphatic epoxy resin, and aliphatic glycidyl ether.
Examples of the melamine-based emulsion include a melamine resin and a modified melamine resin. Further, as the polyolefin-based emulsion, for example, polyethylene resin, polypropylene resin, modified polypropylene resin,
A typical example is an acrylic resin. In the present invention, these may be used alone or in combination of several kinds.

The content ratio of the glass fiber bundle in all the glass fibers (defibrillated glass fiber + glass fiber bundle) in the glass fiber papermaking product is preferably from 10 to 70% by weight, particularly preferably from 30 to 60% by weight. It is. In order to obtain stamping molding materials and molded products with excellent mechanical strength,
The content ratio of the glass fiber bundle needs to be 10% by weight or more. On the other hand, if the content ratio of the glass fiber bundle is too large, the ratio of glass fibers that are not in sufficient contact with the thermoplastic resin in the glass fiber papermaking becomes too large,
Since the static strength such as bending strength decreases, the content ratio of the glass fiber bundle is preferably set to 70% by weight or less.

The content ratio of all glass fibers (defibrillated glass fibers + glass fiber bundles) in the glass fiber sheet varies depending on the specific gravity of the thermoplastic resin used and the addition of other components. When polypropylene is used as the plastic resin, it is usually used so that the content ratio of all glass fibers is 10 to 60% by weight, preferably 20 to 50% by weight, based on the total weight of the glass fiber papermaking product. When the content ratio of all glass fibers is less than 10% by weight, it is impossible to obtain a stamping molding material and a molded product having sufficient rigidity. On the other hand, the content ratio of all glass fibers is 6
If the content exceeds 0% by weight, the thermoplastic resin as a matrix cannot be sufficiently impregnated into the glass fiber at the time of molding into a sheet or at the time of flow molding, and a stamping molding material or a flow molded product having sufficient strength cannot be obtained. There is a risk.

The production of the glass fiber sheet used in the present invention is carried out by mixing glass fibers (defibrillated glass fibers and glass fiber bundles), thermoplastic resin particles, and various components added as necessary in an aqueous medium. Disperse to prepare a dispersion,
By casting this dispersion on a porous support and defoaming through the porous support, a uniform glass fiber paper can be obtained. This glass fiber sheet has a state in which particles of the thermoplastic resin are uniformly dispersed in the aggregate of the glass fibers. In addition, the defibrated glass fiber is defibrated to almost a single fiber state, and constitutes the skeleton of the papermaking body. Since the glass fiber bundle is bundled using a sizing agent that is not substantially dissolved in the aqueous medium, the glass fiber bundle exists in the papermaking body in a bundle state.

The aqueous medium used for the production of this paper is foamed from an aqueous solution containing a surfactant. The surfactant used may be any of anionic, nonionic and cationic surfactants. In particular, sodium dodecylbenzenesulfonate, coconut oil diethanolamide and the like are excellent in dispersibility of raw materials mainly composed of defibrated glass fibers and / or glass fiber bundles and thermoplastic resin while being inexpensive. Are used advantageously.

The concentration of the surfactant in the aqueous medium varies depending on the type of the surfactant used.
The range of from 0.5 to 2% by weight is preferred. If the concentration of the surfactant is too low, it is difficult to obtain fine bubbles suitable for dispersing the raw material, while if the concentration of the surfactant is too high, the effect of the surfactant is saturated and the meaning of increasing the concentration is significant. Disappears.

The content of air in the aqueous medium is preferably 40 to 85% by volume, more preferably 55 to 75% by volume at the time of charging the raw material. It is advantageous if the air content in the aqueous medium at the time of charging the raw materials is in the range of 40 to 85% by volume because the stability of the bubbles and the dispersibility of the raw materials are good. Here, the air content is defined by the following formula when the specific gravity of the aqueous surfactant solution is x and the weight of 1000 ml of foam is Zg. Air content = 100 × (1000−Z / x) / 1000
(capacity%)

The size of the bubbles in the aqueous medium is 10 to 20
It is desirable to be in the range of 0 μm. Bubble size is 1
When it is less than 0 μm, the viscosity of the aqueous medium becomes high, and a large suction pressure is required for defoaming. On the other hand, if the size of the bubbles exceeds 200 μm, the dispersion of the raw materials may be insufficient.

The production of the stamping molding material of the present invention comprises:
A composite laminate including an organic peroxide layer, and a thermoplastic resin layer on the organic peroxide layer, on both surfaces of a glass fiber paper formed by forming a dispersion liquid containing a thermoplastic resin and glass fiber. After forming the body, the method can be performed according to a method including a step of forming the composite laminate into a sheet by heating and pressing. In this method, a thin layer made of a thermoplastic resin may be provided between the surface of the glass fiber sheet and the organic peroxide layer. As a specific embodiment of this method, (1) an organic peroxide is applied to one surface of a film made of a thermoplastic resin, and then a thin film made of a thermoplastic resin is pressed on the applied surface of the organic peroxide. A multi-layer film is formed, and the multi-layer film is laminated via a thin film on both surfaces of a glass fiber paper formed by forming a dispersion liquid containing a thermoplastic resin and glass fiber, thereby forming a composite laminate. After molding, a method comprising a step of heating and pressing the composite laminate to form a sheet. (2) A film made of a thermoplastic resin coated with an organic peroxide on one side, and a glass fiber paper formed by forming a dispersion containing the thermoplastic resin and the glass fiber, on both sides of an organic peroxide. And forming a composite laminate by heating and pressurizing the composite laminate to form a sheet. (3) An organic peroxide layer is formed on both sides of a glass fiber sheet obtained by forming a dispersion containing a thermoplastic resin and glass fiber, and then a thermoplastic resin is formed on the organic peroxide layer. A method comprising forming a resin layer to form a composite laminate, and then heating and pressing the composite laminate to form a sheet. (4) After an organic peroxide is contained in a glass fiber paper formed by forming a dispersion containing a thermoplastic resin and glass fiber, a thermoplastic resin layer is formed on both surfaces of the glass fiber paper. Forming a composite laminate by heating and pressurizing the composite laminate to form a sheet. Is mentioned. Among these methods, the methods (1) and (2) are preferred because they are easy to handle and easy to make products.

Examples of the organic peroxide used in the production of the stamping molding material of the present invention include ketone peroxide, hydroperoxide, diacyl peroxide, dialkyl peroxide, peroxyketal, and the like. Specific examples of the organic peroxide include benzoyl peroxide, acetyl peroxide, di-t-butyl peroxide, t-butyl peroxylaurate, dicumyl peroxide, 1,3-bis (t
-Butylperoxyisopropyl) benzene, 1,4-
Bis (t-butylperoxyisopropyl) benzene,
2,5-dimethyl-2,5-di-t-butylperoxyhexane, 2,5-dimethyl-2,5-di-t-butylperoxyhexyne-3, 2,5-di-t-butyl Peroxyhexane, t-butyl peroxybenzoate,
Octanoyl peroxide, p-menthane hydroperoxide, t-butylmaleic acid, t-butylperoxyacetate and the like can be mentioned.

The organic peroxide used in the present invention preferably has a one-minute half-life temperature of 100 to 250 ° C., particularly preferably a one-minute half-life temperature of 150 to 220 ° C. When the one-minute half-life temperature is lower than 100 ° C., the amount of the organic peroxide that decomposes without reacting with the thermoplastic resin during sheeting described later increases. 250 ° C
If it is higher, the reaction with the thermoplastic resin at the time of sheeting is not sufficient, and the effect is reduced. In the present invention, the one-minute half-life temperature of the organic peroxide refers to a temperature at which the concentration of the organic peroxide is reduced to half the initial concentration in one minute.

The thermoplastic resin film used for forming the thermoplastic resin layer in the production of the glass fiber fiber sheet may be a thermoplastic resin film, for example, a polyolefin resin, a polyester resin, or a polycarbonate resin. Resins, polyamide resins and the like. Specifically, polypropylene, polyethylene and modified products thereof, copolymers, mixtures thereof, and the like, that is, maleic acid-modified polypropylene, maleic anhydride-modified polypropylene, acrylic acid-modified polypropylene, propylene-ethylene copolymer, polypropylene and propylene-
Examples include a mixture of ethylene copolymers, such as polybutylene terephthalate, polyethylene terephthalate, nylon 6, nylon 66, polycarbonate, and acrylonitrile styrene resin. Among these, polypropylene and / or a modified product thereof are most preferable in terms of strength characteristics and price. In addition, the matrix resin of the glass fiber papermaking and the resin of the thermoplastic resin film may be the same or different.

In the method (1) or (2) for producing the stamping molding material of the present invention, the application of the organic peroxide to the thermoplastic resin film may be performed by applying a solid organic peroxide to the thermoplastic resin film. First, after dissolving the organic peroxide in an organic solvent or the like capable of dissolving, it can be carried out according to a conventional method using a coater, a spray or the like. When a liquid organic peroxide is applied, it may be applied to a thermoplastic resin film as it is or after preparing a solution having an appropriate concentration using a solvent. Examples of the organic solvent used include methanol, ethanol, methyl ethyl ketone, and acetone.

The amount of the organic peroxide to be applied to the thermoplastic resin film is based on 100 parts by weight of the glass fiber sheet.
In the range of 0.01 to 10 parts by weight, preferably 0.1 to 1.
The amount is preferably 0 parts by weight. When the amount of the organic peroxide is small, the effect of covering and hiding the glass fiber becomes insufficient, and it is not possible to obtain a stamping molding material that can be molded to obtain a molded article having an excellent appearance. On the other hand, if the amount of the organic peroxide is too large, the strength of the flow molded article is reduced, which is not preferable.

The thickness of the thermoplastic resin film used is 50 μm to 5 mm. If it is less than 50 μm, the handleability is poor, and if it is more than 5 mm, the glass fiber content decreases, and the desired strength cannot be obtained.

A composite laminate is formed by laminating a thermoplastic resin film coated with an organic peroxide on one side such that the coated side or thin film side is on the glass fiber papermaking side. Lamination on the side coated with the peroxide or on the side opposite to the glass fiber papermaking has little effect of improving the appearance. Further, simply laminating the organic peroxide layer on only one surface of the glass fiber papermaking has a small effect of improving the appearance.

As shown in FIG. 1, the composite laminate obtained according to the method (1) or (2) has organic peroxide layers 12 a and 12
b, and has a structure in which thermoplastic resin layers 13a and 13b made of a thermoplastic resin film are laminated on respective surfaces of the organic peroxide layers 12a and 12b.

In this composite laminate, the thickness between the organic peroxide layer 12a and the glass fiber paper 11 and between the organic peroxide layer 12b and the glass fiber paper 11 are 1 mm.
It is preferable that a thin thermoplastic resin layer composed of a thin thermoplastic resin film having a thickness of 50 μm to 50 μm, particularly 5 μm to 20 μm is laminated. The thin thermoplastic resin layer can be formed by further laminating a thin thermoplastic resin film on the surface of the thermoplastic resin film on which the organic peroxide has been applied, and laminating the thin thermoplastic resin film on a glass fiber sheet. Because the thermoplastic resin thin layer is laminated between the organic peroxide layer and the glass fiber papermaking, the organic peroxide is converted into the thermoplastic resin film in the steps of transporting, laminating, and sheeting the composite laminate. This is effective in that a stamping molding material which can be prevented from being detached from the mold and can be subjected to flow molding to obtain a molded article having an excellent appearance can be produced. When a thermoplastic resin film having a thickness of less than 1 μm is used, the organic peroxide is easily released and the film is easily broken. If it exceeds 50 μm, the effect of the organic peroxide is reduced, and the appearance of the molded product is deteriorated.

In the above method (3) or (4), first, an organic peroxide is added to the glass fiber sheet, and then a thermoplastic resin film is laminated on both sides to form a composite laminate. Molded. The addition of an organic peroxide to a glass fiber paper is performed by dissolving the organic peroxide in a solvent capable of dissolving the organic peroxide or dispersing the organic peroxide in a liquid when the organic peroxide is solid. The resulting dispersion can be applied by a conventional method using a coater, a spray or the like. Examples of the organic solvent include methanol, methyl ethyl ketone, acetone and the like. In addition, the powdered organic peroxide can be added as it is to the glass fiber sheet by uniformly spraying. Further, when the organic peroxide is a liquid, it can be applied as it is or adjusted to an appropriate concentration, and applied to a glass fiber sheet.

At this time, the amount of the organic peroxide to be added is in the range of 0.01 to 10 parts by weight, particularly 0.1 to 1.0 part by weight, based on 100 parts by weight of the glass fiber papermaking material. It is preferred to add. If the amount of the organic peroxide added to the glass fiber paper is small, the effect of covering and hiding the glass fiber becomes insufficient, and a stamping molding material that can be molded to obtain a molded article having an excellent appearance is used. I can't get it. On the other hand, if the amount of the organic peroxide is too large, the strength of the molded article is reduced, which is not preferable.

Next, as described above, a thermoplastic resin layer is formed by laminating a thermoplastic resin film on both sides of the glass fiber sheet to which the organic peroxide has been added, and a composite laminate is formed. This thermoplastic resin layer is for improving the appearance of the charged part of the molded product. This thermoplastic resin film may be the same as that used in the method (1) or (2).

As shown in FIG. 2, the composite laminate obtained according to the method (3) or (4) comprises a thermoplastic resin film on both sides of a glass fiber paper 21 to which an organic peroxide has been added. Thermoplastic resin layers 22a and 22
2b has a laminated structure.

The composite laminate having the structure shown in FIG. 1 or 2 obtained by the above-described method is heated and pressed to form a sheet, and as shown in FIG.
A layer or film 32a made of a thin thermoplastic resin on both surfaces
And 32b can be produced. At this time, it is considered that the organic peroxide is decomposed by heating during molding and substantially does not remain.

The heating temperature in forming the composite laminate into a sheet is not lower than the melting point of the thermoplastic resin constituting the thermoplastic resin layer and not higher than the decomposition temperature. For example, when the thermoplastic resin is polypropylene, the heating temperature is preferably 170 to 230 ° C, particularly preferably 190 to 210 ° C. 230
If the temperature exceeds ℃, coloring due to decomposition of polypropylene occurs.

The pressure when the composite laminate is pressed is as follows:
In order to obtain a dense stamping molding material, 0.5 to 5
It is preferably 0 kgf / cm ² . Excessive pressure can cause glass fiber breakage. If the pressure is too low, the impregnation of the thermoplastic resin into the glass fiber becomes insufficient, which may lead to poor appearance of the molded product and a decrease in mechanical strength.

Further, the stamping molding material of the present invention may contain additives such as antioxidants, light stabilizers, metal deactivators, flame retardants, carbon black and the like, coloring agents and the like. These additives or coloring agents are added, for example, by a spray or curtain coater during the process of previously blending or coating with a granular thermoplastic resin used in the production of glass fiber papermaking or forming into a sheet. By doing so, it can be contained in the stamping molding material.

The stamping molding material of the present invention can be molded into a desired molded product according to a known method. For example, as described with reference to FIGS. 4 (A) and 4 (B), the stamping molding material of the present invention is heated to a temperature not lower than the melting point or softening point of the thermoplastic resin which is the matrix of the glass fiber papermaking but not higher than the decomposition temperature. Thereafter, the molding die is placed on the lower die, the upper die is closed, and pressure is applied to form a molded product having a desired shape. When the thermoplastic resin used as the matrix of the glass fiber paper is polypropylene, the heating temperature is preferably 170 to 230 ° C.,
Especially preferably, it is 190-210 degreeC. If the temperature exceeds 230 ° C., coloring and strength reduction may occur due to decomposition of polypropylene. The molding pressure varies depending on the shape of the molded product, but is usually 10 to 500 kg / cm ² . Excessive pressure can cause glass fiber breakage.
If the pressure is too low, the impregnation of the resin into the glass fibers becomes insufficient, which may lead to poor appearance of the molded product and a decrease in mechanical strength. Further, the mold temperature may be a temperature not higher than the freezing point of the thermoplastic resin. From the viewpoint of handling properties and productivity, the temperature is usually from room temperature to 60 ° C.

[0070]

EXAMPLES Examples and comparative examples of the present invention will be shown below.
The present invention will be described more specifically.

Example 1 53% by weight of polypropylene particles (average particle size: 500 μm), 23.5% by weight of defibrated glass fiber (fiber diameter: 11 μm), 23.5% by weight of glass fiber bundle by dry weight (Hereinafter referred to as “web”) having a composition of (weight per unit area: 2000 g / m 2)
² ) was produced by a papermaking method. Next, as an organic peroxide on one side of a polypropylene film (thickness: 200 μm),
1,3-bis- (t-butylperoxyisopropyl)
A solution of benzene (1 minute half-life temperature: 183 ° C.) in methyl ethyl ketone was applied and dried to form an organic peroxide layer having an adhesion amount of 2 g / m ² .

Each of the two polypropylene films was laminated on both sides of the web such that the organic peroxide layer was on the web side to obtain a composite laminate. After heating this composite laminate at 210 ° C., it was placed between press platforms cooled to 25 ° C. and pressed into a sheet at a pressure of 3 kgf / cm ² to produce a stamping molding material.

The obtained stamping molding material (100 ×
100mm) 5 sheets with a far infrared heater with a surface temperature of 2
Heated to 10 ° C. Next, five heated molding materials were laminated on a mold at 25 ° C., and the pressure was 30 kgf / cm.
Flow molding was performed in ² . The dimensions of the obtained flow molded product are
It was length 200 x width 200 x thickness 2 mm. The appearance of the flow molded product was observed and evaluated according to the following criteria. ○ No appearance of glass fiber bundles at all, good appearance △ Glass fiber bundles are slightly raised × Many glass fiber bundles are raised, appearance is poor

Further, a bending test piece and an Izod impact test piece were cut out from the obtained flow molded product and were subjected to JIS K7
The flexural modulus, flexural strength and Izod impact strength were measured in accordance with J.203 and JIS K7110.
Table 1 shows the results.

(Example 2) The content ratio of the defibrated glass fiber and the glass fiber bundle in the web was 33% by weight, respectively.
A stamping molding material was produced in the same manner as in Example 1, except that the amount was 14% by weight, and flow molding was performed. The appearance, flexural modulus, bending strength and Izod impact strength of the obtained flow molded product were evaluated. Or measured. Table 1 shows the results.

Example 3 The amount of 1,3-bis- (t-butylperoxyisopropyl) benzene attached was 4 g / m
Except that the polypropylene film of No. ² was prepared and used, a stamping molding material was produced in the same manner as in Example 1 and flow molding was performed, and the appearance, flexural modulus, and bending strength of the obtained flow molded product were obtained. And the Izod impact strength was evaluated or measured. Table 1 shows the results.

Example 4 The content ratio of the defibrated glass fiber and the glass fiber bundle in the web was 19% by weight, respectively.
And 28% by weight, and the attached amount of 1,3-bis- (t-butylperoxyisopropyl) benzene was 4 g /
except that created the polypropylene film m ² is to produce a stamping material in the same manner as in Example 1, further subjected to flow forming, resulting flow molded article appearance, flexural modulus, flexural strength and Izod impact strength Was evaluated or measured. Table 1 shows the results.

Example 5 The amount of 1,3-bis- (t-butylperoxyisopropyl) benzene deposited was 0.2 g.
/ M ² , a stamping molding material was produced in the same manner as in Example 1 except that the polypropylene film was used, followed by flow molding, and the appearance, flexural modulus, The bending strength and Izod impact strength were evaluated or measured. Table 1 shows the results.

Example 6 Isobutyl peroxide (1 minute half-life temperature: 89 ° C.) as an organic peroxide was applied as a liquid to form an organic peroxide layer having an adhesion amount of 2 g / m ² . Except using polypropylene film,
A stamping molding material was produced in the same manner as in Example 1,
Further, flow molding was performed, and the appearance, flexural modulus, bending strength and Izod impact strength of the obtained flow molded product were evaluated or measured. Table 1 shows the results.

Example 7 One side of a 200 μm thick polypropylene film was coated with 1,3-bis- (t-butylperoxyisopropyl) benzene (1 minute half-life temperature: 183 ° C.) as an organic peroxide. A methyl ethyl ketone solution was applied and dried to form an organic peroxide layer having an adhesion amount of 2 g / m ² . Next, a thin film of polypropylene having a thickness of 15 μm was laminated on the organic peroxide layer and pressed at 170 ° C. to form a multilayer film. A stamping molding material was produced in the same manner as in Example 1 except that each of the two multilayer films was laminated on both sides of the web, with the thin film side as the web side, and further subjected to flow molding. The appearance, flexural modulus, flexural strength and Izod impact strength of the obtained flow molded product were evaluated or measured. Table 1 shows the results.

(Comparative Example 1) A stamping molding material was produced in the same manner as in Example 1 except that a polypropylene film to which no organic peroxide was applied was used, followed by flow molding, and the appearance of the obtained flow molded product. , Flexural modulus,
The bending strength and Izod impact strength were evaluated or measured. Table 1 shows the results.

(Comparative Example 2) A web having a dry weight of 60% by weight of polypropylene particles, 20% by weight of defibrated glass fibers, and 20% by weight of a glass fiber bundle (basis weight: 2000 g / m ² )
Was produced by a papermaking method. Next, without laminating the polypropylene film on the web, using the web as it is as the stamping molding material, flow molding was performed in the same manner as in Example 1, and the appearance, flexural modulus,
The bending strength and Izod impact strength were evaluated or measured. Table 1 shows the results.

[0083]

[Table 1]

Example 8 53% by weight of polypropylene particles (average particle diameter: 500 μm), 23.5% by weight of defibrated glass fiber (fiber diameter: 11 μm) and 23.5% by weight of glass fiber bundle by dry weight (Weight per unit area: 2000 g / m ² ) was manufactured by a papermaking method. Next, 1,3-bis (t-butylperoxyisopropyl) benzene (1 minute half-life temperature: 183) was used as an organic peroxide.
C) A dispersion of particles dispersed in water was sprayed onto the web and added. At this time, the amount of the organic peroxide added to the web was 0.4 parts by weight based on 100 parts by weight of the web.

Then, a polypropylene film having a thickness of 200 μm was laminated on both sides of the web to obtain a composite laminate. After heating this composite laminate to 210 ° C, 25 ° C
3 kgf / cm ²
A stamping molding material was manufactured by press-molding into a sheet at the pressure described above.

Using the obtained stamping molding material,
Flow molding was performed in the same manner as in Example 1, and the obtained flow molding was performed, and the appearance, flexural modulus, bending strength, and Izod impact strength of the obtained flow molded product were evaluated or measured. Table 2 shows the results.

Example 9 The content ratio of the defibrated glass fiber and the glass fiber bundle in the web was 28% by weight, respectively.
A stamping molding material was produced in the same manner as in Example 8 except that the amount was 12% by weight. Using the obtained stamping molding material, flow molding was performed in the same manner as in Example 1, and the obtained flow molding was performed. The appearance, flexural modulus, bending strength, and Izod impact strength of the obtained flow molded product were obtained. Was evaluated or measured. Table 2 shows the results.

Example 10 A stamping molding material was produced in the same manner as in Example 8, except that the organic peroxide was added in an amount of 0.04 parts by weight based on 100 parts by weight of the web. did. Next, using the obtained stamping molding material, flow molding was performed in the same manner as in Example 1, the obtained flow molding was performed, and the appearance, flexural modulus, bending strength, and bending strength of the obtained flow molded product were measured. The Izod impact strength was evaluated or measured. Table 2 shows the results.

(Example 11) A stamping molding material was produced in the same manner as in Example 8, except that the content ratios of the defibrated glass fiber and the glass fiber bundle in the web were 16% by weight and 24% by weight, respectively. . Next, using the obtained stamping molding material, in the same manner as in Example 1,
Flow molding was performed, the obtained flow molding was performed, and the appearance, flexural modulus, bending strength and Izod impact strength of the obtained flow molded product were evaluated or measured. Table 2 shows the results.

Example 12 A stamping molding material was produced in the same manner as in Example 8, except that the organic peroxide was added in an amount of 0.04 parts by weight based on 100 parts by weight of the web. did. Next, using the obtained stamping molding material, flow molding was performed in the same manner as in Example 1, the obtained flow molding was performed, and the appearance, flexural modulus, bending strength, and bending strength of the obtained flow molded product were measured. The Izod impact strength was evaluated or measured. Table 2 shows the results.

Example 13 Except that isobutyl peroxide (1 minute half-life: 89 ° C.) was added as an organic peroxide in a liquid state to 0.4 parts by weight with respect to 100 parts by weight of a web. Produced a stamping molding material in the same manner as in Example 8. Next, using the obtained stamping molding material, flow molding was performed in the same manner as in Example 1, the obtained flow molding was performed, and the appearance, flexural modulus, bending strength, and bending strength of the obtained flow molded product were obtained. The Izod impact strength was evaluated or measured. Table 2 shows the results.

[0092]

[Table 2]

[0093]

According to the stamping molding material of the present invention, a molded article having an excellent appearance can be obtained by flow molding. Further, since the stamping molding material of the present invention has excellent fluidity, it is suitable as a molding material for molded articles having complicated shapes such as ribs and bosses. For example, battery trays, concrete formwork,
It is suitable as a molding material for housings of pallets, home appliances or office equipment.

Further, according to the method for producing a stamping molding material of the present invention, the stamping molding material of the present invention having the above-mentioned features can be produced.

Further, the sheet for stamping molding material of the present invention can be suitably used for the stamping molding material of the present invention.

Furthermore, the flow molded article of the present invention is obtained by subjecting the stamping molding material to flow molding and has an excellent appearance.

[Brief description of the drawings]

FIG. 1 is a schematic cross-sectional view illustrating an example of the structure of a composite laminate in the production of a stamping molding material according to the present invention.

FIG. 2 is a schematic cross-sectional view illustrating another example of the structure of the composite laminate in the production of the stamping molding material of the present invention.

FIG. 3 is a schematic cross-sectional view illustrating a structural example of a stamping molding material of the present invention.

FIGS. 4A and 4B are schematic diagrams for sequentially explaining the steps of a flow molding method.

FIG. 5 is a view for explaining a state in which a stamping molding material in flow molding is placed on a lower mold.

FIG. 6 is a view for explaining a flow portion and a charge portion of a flow molded product formed by flow molding using the mold shown in FIG. 5;

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 11 Glass fiber maker 12a, 12b Organic peroxide layer 13a, 13b Thermoplastic resin layer 21 Organic peroxide containing glass fiber maker 22a, 22b Thermoplastic resin layer 31 Glass fiber maker 32a, 32b It consists of thermoplastic resins. Layer or film 33 Stamping molding material 41 Stamping molding material 44a Charge section 44b Flow section 42 Lower mold 43 Upper mold 44 Molded product

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI B32B 27/32 C08J 5/08 C08J 5/08 B29C 67/14 G // B29K 105: 06 309: 08 B29L 9:00 (72 ) Inventor Yukio Nagashima 1 Kawasaki-cho, Chuo-ku, Chiba City, Chiba Prefecture Inside Kawasaki Steel Research Institute Co., Ltd. Company Chiba Works

Claims (27)

[Claims] Claims: 1. A glass fiber paper comprising a thermoplastic resin,
A stamping molding material obtained by heating and pressing a composite laminate having a thermoplastic resin layer laminated on both sides of the glass fiber sheet via an organic peroxide layer to form a sheet. 2. The stamping molding material according to claim 1, wherein a thin thermoplastic resin layer having a thickness of 1 to 50 μm is provided between the organic peroxide layer and the glass fiber papermaking. 3. A composite laminate comprising a glass fiber paper containing a thermoplastic resin and containing an organic peroxide, and thermoplastic resin layers laminated on both surfaces of the glass fiber paper is heated and heated. Stamping molding material formed by pressing to form a sheet. 4. The thermoplastic resin layer has a thickness of 50 μm to 5 μm.
The stamping molding material according to any one of claims 1 to 3, wherein 5. An organic peroxide, comprising:
Claims 1 to 10 parts by weight, based on parts by weight.
5. The stamping molding material according to any one of 4. 6. The stamping molding material according to claim 1, wherein the organic peroxide has a one-minute half-life temperature of 100 to 250 ° C. 7. The glass fiber bundle according to claim 1, wherein 10 to 70% by weight of the glass fiber contained in the glass fiber paper is a glass fiber bundle treated with a sizing agent which is insoluble in an aqueous medium used in the paper making method. The stamping molding material as described. 8. The stamping molding material according to claim 1, wherein the thermoplastic resin and the constituent resin of the thermoplastic resin layer are polypropylene. 9. The stamping molding material according to claim 2, wherein the constituent resin of the thin thermoplastic resin layer is polypropylene. 10. An organic peroxide layer, a thermoplastic resin layer on the organic peroxide layer, on both sides of a glass fiber paper formed by forming a dispersion containing a thermoplastic resin and glass fiber. And forming the composite laminate into a sheet by heating and pressurizing the composite laminate to form a sheet. 11. The method for producing a stamping molding material according to claim 10, wherein a thin thermoplastic resin layer having a thickness of 1 to 50 μm is formed between the organic peroxide layer and the glass fiber papermaking body. 12. A multilayer film is formed by applying an organic peroxide to one surface of a film made of a thermoplastic resin and then pressing a thin film made of a thermoplastic resin on the surface to which the organic peroxide is applied. After forming a composite laminate by laminating the multilayer film on both sides of a glass fiber papermaking product obtained by forming a dispersion liquid containing a thermoplastic resin and glass fiber via a thin film, and then forming a composite laminate, A method for producing a stamping molding material comprising a step of heating and pressurizing to form a sheet. 13. A film made of a thermoplastic resin coated with an organic peroxide on one side, and an organic peroxide film formed on both sides of a glass fiber sheet formed by forming a dispersion containing the thermoplastic resin and glass fibers. And forming a composite laminate by heating and pressurizing the composite laminate to form a sheet. 14. An organic peroxide layer is formed on both sides of a glass fiber article obtained by sheeting a dispersion containing a thermoplastic resin and glass fiber. A method for producing a stamping molding material, comprising a step of forming a thermoplastic resin layer to form a composite laminate, and then heating and pressing the composite laminate to form a sheet. 15. An organic peroxide is added to a glass fiber paper obtained by forming a dispersion containing a thermoplastic resin and glass fiber, and then a thermoplastic resin layer is formed on both sides of the glass fiber paper. A method for producing a stamping molding material, comprising a step of forming and forming a composite laminate, and then heating and pressing the composite laminate to form a sheet. 16. The thermoplastic resin layer having a thickness of 50 μm or less.
16. A device as claimed in claim 10, 11, 14 and 15 of 5 mm.
The method for producing a stamping molding material according to any one of the above. 17. A film comprising the thermoplastic resin,
The method for producing a stamping molding material according to claim 12, wherein the thickness is 50 μm to 5 mm. 18. An organic peroxide is added to a glass fiber papermaking product 10.
The method for producing a stamping molding material according to any one of claims 10 to 17, wherein 0.01 to 10 parts by weight is used relative to 0 parts by weight. 19. The organic peroxide having a half-life temperature of 100 to 250 ° C. for one minute.
The method for producing a stamping molding material according to any one of the above. 20. A glass fiber bundle treated with a sizing agent insoluble in an aqueous medium used in a papermaking method, wherein 10 to 70% by weight of glass fiber contained in the glass fiber papermaking body is treated.
20. The method for producing a stamping molding material according to any one of the items 19 to 19. 21. The thermoplastic resin and the constituent resin of the thermoplastic resin layer are polypropylene.
The method for producing a stamping molding material according to any one of the above. 22. The thermoplastic resin as a constituent of the thin thermoplastic resin layer is polypropylene.
2. The method for producing a stamping molding material according to any one of 1. 23. A sheet for a stamping molded material having an organic peroxide layer on one surface of a thermoplastic resin sheet. 24. The thermoplastic resin sheet according to claim 20, wherein the thickness of the thermoplastic resin sheet is 50 μm or less.
24. The sheet for a stamping molded material according to claim 23, having a thickness of 5 mm. 25. The sheet according to claim 23, further comprising a thin thermoplastic resin layer having a thickness of 1 to 50 μm on the organic peroxide layer. 26. The organic peroxide according to claim 1, wherein the half-life is 10 minutes.
The sheet for a stamping material according to any one of claims 23 to 25, which has a temperature of 0 to 250 ° C. 27. A flow molded product obtained by subjecting the stamping molding material according to claim 1 to flow molding.