JP2017043723A - Liquid resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid resin composition that can be used for a variety of applications and is reduced in inflammability during heating.SOLUTION: The liquid resin composition has a resin component dissolved in a solvent component in which the solvent component includes liquid bromine and the resin component includes a thermoplastic resin soluble in the liquid bromine. The solvent component may include an organic solvent with liquid bromine. An adhesively bonded product bonded by an adhesive including the liquid resin composition and an adhesive bonding method are provided. A method for producing a fiber-reinforced resin molded product comprises impregnating the liquid resin composition into a structure including fibers or bonding the composition on the structure and solidifying the composition.SELECTED DRAWING: None

Description

  The present invention relates to a liquid resin composition and use thereof.

Bromine is generally used as a reaction reagent for brominating or flame-retarding organic compounds and synthetic resins. Examples of uses other than the reaction reagent for bromine include, for example, a surface treatment method in which bromine is brought into contact with the surface of a molded body made of an aromatic polymer having a ketone bond in the main chain and the surface of the molded body is etched (Patent Document 1). Including a closed pressure chamber for storing a solute, a solvent chamber for storing a solvent, and a semipermeable partition interposed between them and allowing only the solvent to pass therethrough, in a system for generating hydrostatic pressure energy. Using bromine and solutes such as NaCl, AlCl ₃ , LiCl, solvent-soluble acid, base, metal salt of inorganic acid, metal salt of organic acid, chloride, sulfate, nitrate, saccharide, colloid penetrant, inorganic or organic Energy generation system using polymer, saccharide, alcohol and mixture thereof (Patent Document 2, Claims 1, 36 to 37), bromine on the surface of synthetic resin molding And then bringing the inorganic peroxide into contact with each other, activating or roughening the surface of the synthetic resin molded body by reaction of bromine and inorganic peroxide, and then plating the surface of the synthetic resin molded body by electroless plating There has been proposed a plating method (Patent Document 3) and the like.

  However, bromine used in the surface treatment method of Patent Document 1 is not a liquid but a gas. The energy generation system disclosed in Patent Document 2 generates liquid hydrostatic energy by moving liquid bromine in a solvent chamber through a semipermeable partition into a closed pressure chamber and increasing the internal pressure of the closed pressure chamber. The solution in which the solute is dissolved is not used industrially. The plating method of Patent Document 3 is to etch the surface of a resin molded body by reaction of bromine and an inorganic peroxide. Similar to the energy generation system of Patent Document 2, a solution in which a solute is dissolved in liquid bromine is used. It is not used industrially. Further, Patent Documents 1 to 3 do not disclose any dissolution of the resin component in liquid bromine.

  On the other hand, a resin solution obtained by dissolving a thermoplastic resin in an organic solvent together with other components has been conventionally used as a paint, an adhesive, and the like, and also used as a raw material for producing a fiber-reinforced resin molded body. . When the resin solution is used as an adhesive, for example, the resin solution is generally applied to an object to be coated, and the obtained coating film is dried by heating to obtain a solidified layer. However, since the resin solution contains a relatively large amount of an organic solvent having a high risk of ignition, it is necessary to carry out strict safety management when forming a solidified layer by heating and drying the coating film, This contributes to a longer process time and higher cost. Further, a solidified layer formed from a conventional resin solution is not at a level that can sufficiently satisfy the adhesion to the surface of an object to be coated. In addition, instant adhesives containing organic compounds that are cured by reaction with moisture in the air, such as cyanoacrylate, are often used, but adhesives with even higher adhesive strength are desired.

  In order to obtain a fiber reinforced resin molded article containing a thermoplastic resin, generally, the thermoplastic resin is heated to a temperature of around 200 ° C. or higher and melted, and the resulting melt is used as a fiber. It is necessary to impregnate the structure. However, since the thermoplastic resin melt has a relatively high viscosity, impregnation of the fiber structure may be uneven or insufficient, and the melt usually has a temperature of 100 ° C. or higher. Therefore, it cannot be said that the handling property is good. In addition, when the fiber structure is impregnated with the resin solution and the organic solvent is removed by heating, the risk of ignition is high as described above, so extremely strict process control is required, and fiber reinforced resin molding It is difficult to keep body manufacturing costs low.

JP-A-7-118417 JP-T-2006-528740 JP-A-2-277778

  The objective of this invention is providing the liquid resin composition which contains a thermoplastic resin and can be used for various uses.

  As a result of intensive studies to solve the above problems, the present inventors can dissolve many types of thermoplastic resins by using a solvent component containing liquid bromine as a solvent for dissolving thermoplastic resins. Found that the risk of ignition when volatilizing the solvent by heating or the like is mitigated, and that a liquid resin composition that can be suitably used for various applications can be obtained by selecting the type of thermoplastic resin. It came to be completed.

  That is, the present invention provides a liquid resin composition of (1) to (5), an adhesive product of (6) to (8), an adhesive method of (9), and a method for producing a fiber-reinforced resin molded product of (10). I will provide a.

(1) A liquid resin composition in which a resin component is dissolved in a solvent component, wherein the solvent component contains liquid bromine and the resin component contains a thermoplastic resin that is soluble in liquid bromine.
(2) The liquid resin composition according to (1), wherein the solvent component further comprises an organic solvent compatible with liquid bromine.
(3) The liquid resin composition according to the above (2), comprising 0.1 to 30% by weight of a resin component, 0.5 to 60% by weight of liquid bromine, and 35 to 95% by weight of an organic solvent.
(4) The thermoplastic resin is at least one selected from the group consisting of polymethyl (meth) acrylate, polystyrene, styrene resin, ABS resin, polycarbonate resin, polyester resin, polyamide resin, polyolefin resin, and modified polyolefin resin. The liquid resin composition according to any one of (1) to (3) above.
(5) The organic solvent is at least one selected from the group consisting of aromatic hydrocarbons, alicyclic hydrocarbons, chain saturated hydrocarbons, acetate esters, ketones, and alcohols, The liquid resin composition according to any one of (2) to (4).
(6) One article, another article, and an adhesive layer that is interposed between the one article and the other article and bonds them, and the adhesive layer is as described in (1) to (5) above An adhesive, which is a solidified layer of any liquid resin composition.
(7) The adhesive according to (6) above, wherein at least the surface layer of one article and another article is made of the same or different kind of thermoplastic resin.
(8) The first layer which is interposed between one article and the adhesive layer, and is mixed with the thermoplastic resin contained in the one article and the thermoplastic resin contained in the adhesive layer, and / or adhered to another article. The adhesive according to (7), further comprising a second layer interposed between the layer and a mixture of a thermoplastic resin contained in another article and a thermoplastic resin contained in the adhesive layer.
(9) A step of applying the liquid resin composition of any one of (1) to (5) to one article, and a step of bringing another article into close contact with the surface of the one article on which the liquid resin composition is applied. And a step of solidifying the liquid resin composition.
(10) Fiber reinforced resin molding comprising the steps of impregnating or adhering the liquid resin composition of any one of (1) to (5) above to a structure containing fibers, and a step of solidifying the liquid resin composition Body manufacturing method.

  According to the present invention, there is provided a liquid resin composition comprising a liquid bromine as a solvent component and a thermoplastic resin which can be dissolved in liquid bromine as a resin component. The liquid resin composition has little risk of ignition even when heated, for example, and can be suitably used as, for example, an adhesive or a paint, and can also be used for producing a fiber-reinforced resin molded article.

  The liquid resin composition of the present invention is obtained by dissolving a resin component in a solvent component, and includes a liquid bromine as a solvent component and an organic solvent compatible with liquid bromine as necessary, and a liquid as a resin component. Contains thermoplastic resin soluble in bromine. A liquid resin composition according to a preferred embodiment includes liquid bromine, an organic solvent, and a resin component, and a liquid resin composition according to a more preferred embodiment includes 0.5 to 60% by weight of liquid bromine and 35 to 95 of an organic solvent. % By weight, and 0.1 to 30% by weight of the resin component. Hereinafter, each component of the liquid resin composition of the present invention will be described in more detail.

  Liquid bromine is liquid at room temperature, has no flash point, and has a high ability to dissolve thermoplastic resins. Since liquid bromine does not have a flash point, even if the content of liquid bromine in the liquid resin composition of the present invention is relatively small, the flammability of the liquid resin composition can be relatively greatly reduced, The coating film or layer of the liquid resin composition can be heated without strict process control and solidified safely and at low cost. Moreover, since there is little danger of ignition, it becomes possible to shorten the time required for solidified layer formation by raising the heating temperature of a coating film or a layer.

  Further, by using liquid bromine, an article to be coated or an article to be bonded (hereinafter referred to simply as “solidified layer”) formed by drying and solidifying the liquid resin composition of the present invention. These may be simply referred to as “articles”) to improve the adhesion of the solidified layer to the surface. This is considered to be due to, for example, an etching effect on the article surface by liquid bromine.

  Further, when at least the surface layer portion of the article is made of a thermoplastic resin soluble in liquid bromine (preferably a molded body of a thermoplastic resin soluble in liquid bromine), the liquid resin of the present invention is used for the article. When the composition is applied and the obtained coating film is dried, a solidified layer made of the thermoplastic resin (resin component A) contained in the liquid resin composition is formed on the surface of the article, and liquid bromine is formed in the article. By dissolving at least a part of the thermoplastic resin (resin component B) in the surface layer portion, a bonding layer in which the resin components A and B are mixed is formed. It is considered that the bonding layer is interposed between the article surface and the solidified layer, and remarkably improves the adhesion of the solidified layer to the article. In addition, since it is thought that a joining layer is formed in the area | region of a micron order, it does not impair the external appearance and surface smoothness of a coated article or an adhesive article.

In addition, it is easy to impart a plurality of characteristics and functions to the solidified layer by dissolving and alloying two or more thermoplastic resins using the dissolving ability of liquid bromine in thermoplastic resins.
As liquid bromine, a commercially available product can be used without particular limitation, and a regenerated product may be used.

  In the liquid resin composition of the present invention, only liquid bromine may be used as the solvent component. However, since liquid bromine has a relatively large increase in viscosity due to dissolution of the thermoplastic resin, the handling properties of the liquid resin composition, etc. In consideration of the above, the content of liquid bromine is preferably 0.5 to 60% by weight, more preferably 3 to 30% by weight, and still more preferably 5 to 20% by weight with respect to the total amount of the liquid resin composition .

  When the liquid resin composition contains liquid bromine within the above range, it becomes possible to sufficiently dissolve many types of thermoplastic resins while maintaining good handling properties of the liquid resin composition. Applications of the resin composition are expanded. In addition, the risk of ignition during heating is mitigated, and heating at a higher temperature is possible as compared with the case where the solvent component is composed only of an organic solvent, so the solidified layer of the thermoplastic resin contained in the liquid resin composition Can be obtained in a relatively short time, and the cost can be reduced.

  If the content of liquid bromine is less than 0.5% by weight, the adhesion of the solidified layer made of the liquid resin composition of the present invention to various articles becomes insufficient, and the solvent component can dissolve thermoplastic resin. , And the effect of alleviating the risk of ignition tends to be insufficient. If it exceeds 60% by weight, the handling property due to the increase in the viscosity of the liquid resin composition, and hence the applicability of the product to the article, is greatly reduced. There is a tendency for the application range of things to narrow.

  As the organic solvent, those capable of dissolving a thermoplastic resin and compatible with liquid bromine can be used without particular limitation. For example, aromatic hydrocarbons such as benzene, toluene, xylene, tetralin, decalin, cyclohexane , Cycloaliphatic hydrocarbons such as cyclohexanone, chain saturated hydrocarbons such as n-butane, n-pentane, n-hexane, n-hebutane, n-octane, gasoline, coal tar naphtha, petroleum ether, petroleum naphtha , Petroleum benzine, turpentine oil, mineral spirits, mixtures of aliphatic and aromatic hydrocarbons such as thinner, acetates such as ethyl acetate, butyl acetate and isobutyl acetate, ketones such as methyl ethyl ketone, acetone and methyl isobutyl ketone , Methanol, ethanol, n-propanol, isopropa Lumpur, n- butyl, isobutyl, and alcohols such as tert- butyl. Among these, toluene, xylene, cyclohexane, thinner and the like are preferable from the viewpoint of achieving the handling property of the liquid resin composition and the relaxation of the flammability of the liquid resin composition at a high level and in a well-balanced manner. An organic solvent can be used individually by 1 type or in combination of 2 or more types as needed. As these organic solvents, commercially available products can be used without particular limitation, and recycled products may be used.

  The content of the organic solvent in the liquid resin composition is not particularly limited. However, in consideration of handling properties of the liquid resin composition, relaxation of flammability during heating, etc., preferably 40 to the total amount of the liquid resin composition. It is 95 weight%, More preferably, it is 50-95 weight%, More preferably, it is 60-90 weight%. When the content of the organic solvent is within the above range, liquid bromine relaxes the flammability of the organic solvent while maintaining good handling properties of the liquid resin composition, and the flammability of the liquid resin composition as a whole is improved. Can be reduced.

  When the content of the organic solvent is less than 40% by weight, the handling property of the liquid resin composition is lowered, resulting in insufficient uniformity of the coating film formed from the liquid resin composition. The application range of the resin composition tends to be narrowed, and when it exceeds 95% by weight, the content of liquid bromine and / or the resin component is relatively reduced, so an article of a solidified layer formed from the liquid resin composition There is a tendency that the adhesion to the surface is lowered, and the flammability of the organic solvent by liquid bromine is insufficient, and the flammability of the liquid resin composition is increased.

  As the thermoplastic resin, any conventionally known resin can be used without particular limitation as long as it is soluble in liquid bromine. A thermoplastic resin can be suitably selected according to the use of a liquid resin composition. Examples of the thermoplastic resin that can be suitably used in the liquid resin composition of the present invention include polymethyl methacrylate, polystyrene, styrene resin, ABS resin, polycarbonate resin, polyester resin, polyamide resin, polyolefin resin, and modified polyolefin resin. Can be mentioned. These thermoplastic resins can be used individually by 1 type or in combination of 2 or more types as needed. As these thermoplastic resins, commercially available products can be used without particular limitation.

  In a preferred embodiment of the present invention, a modified polyolefin resin and another thermoplastic resin are used in combination. With this combination, the adhesion between the solidified layer formed from the liquid resin composition and the surface of the article can be further enhanced. In addition, it is estimated that such an effect is acquired because the modified polyolefin resin forms a chemical bond with the article surface.

  The modified polyolefin resin is a polyolefin resin that is given polarity by substituting a halogen atom such as a chlorine atom and / or an organic functional group into the polyolefin resin. Although it does not specifically limit as polyolefin resin used as the main raw material of modified polyolefin resin, For example, polyethylene, a polypropylene, a propylene- alpha-olefin copolymer, ethylene-vinyl acetate copolymer etc. are mentioned. The α-olefin in the propylene-α-olefin copolymer is not particularly limited, but ethylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 4-methyl-1-pentene, and the like. 1 type or 2 types or more can be used. Examples of the organic functional group include unsaturated carboxylic acid groups such as maleic acid groups and maleic anhydride groups, hydroxyl groups, (meth) acrylic groups, and (meth) acrylic ester groups. As the modified polyolefin resin, commercially available products can be used without any particular limitation.

  Among the above-mentioned modified polyolefin resins, from the viewpoint of further improving the adhesion of the solidified layer formed from the liquid resin composition of the present invention to the article, chlorinated polyolefin resin, acid-modified polyolefin resin, acid-modified chlorinated polyolefin resin At least one selected from the group consisting of an acrylic-modified polyolefin resin and an acrylic-modified chlorinated polyolefin resin is preferable, and an acrylic-modified chlorinated polyolefin resin is more preferable.

  When the modified polyolefin resin and other thermoplastic resin are used in combination, the use ratio thereof is not particularly limited, but the content of the other thermoplastic resin is preferably 1 to 50% by weight, more preferably based on the total amount of the resin component. Is 3 to 35% by weight, more preferably 5 to 30% by weight, and the content of the modified polyolefin resin is preferably 45 to 85% by weight, more preferably 50 to 75% by weight, still more preferably 55 to 70% by weight. It is.

  Further, the content of the resin component in the liquid resin composition is not particularly limited, but is preferably 0.1 to 30 with respect to the total amount of the liquid resin composition from the viewpoint of reduction in handling properties due to increase in viscosity of the liquid resin composition. % By weight, more preferably 0.5 to 20% by weight, still more preferably 1 to 15% by weight. When the content of the resin component is within the above range, the solidified layer obtained by heating and drying the liquid resin composition can be sufficiently imparted with functionality utilizing the characteristics of the thermoplastic resin. Since the resin composition has good handling properties, the application range of the liquid resin composition can be expanded.

  In addition, if content of a resin component is less than 0.1 weight%, there exists a tendency which cannot fully utilize the characteristic of a thermoplastic resin. On the other hand, if it exceeds 30% by weight, the handling property of the liquid resin composition decreases due to the increase in viscosity, but it may be usable depending on the application.

  The liquid resin composition of the present invention can be obtained by mixing liquid bromine, a thermoplastic resin, and, if necessary, an organic solvent, and dissolving the thermoplastic resin in liquid bromine or a mixture of liquid bromine and an organic solvent. However, when an organic solvent is used together with liquid bromine, from the viewpoint of obtaining a liquid resin composition that is a homogeneous resin solution, the thermoplastic resin is dissolved in liquid bromine, and the resulting solution and the organic solvent are mixed. Is preferred. Although this series of steps may be performed at room temperature, it is preferable that the liquid resin composition is obtained as a more homogeneous resin solution by heating at about 40 to 50 ° C.

  The liquid resin composition of the present invention thus obtained can be used for the following applications, for example.

  The liquid resin composition of the present invention is used as an adhesive. That is, according to the present invention, an adhesive containing a liquid resin composition, an adhesive produced using the adhesive, and an adhesion method using the adhesive are provided.

  The adhesive of the present invention can contain a general adhesive additive as long as the liquid resin composition is an active ingredient and the physical properties of the liquid resin composition are not impaired. As the thermoplastic resin contained in the liquid resin composition, a thermoplastic resin that can be dissolved in liquid bromine can be used without particular limitation. Among them, for example, polymethyl methacrylate, (meth) acrylic resin, polystyrene, styrene resin ABS resin, polycarbonate resin, polyester resin, polyamide resin, polyolefin resin, modified polyolefin resin, and the like are preferable, and polymethyl methacrylate, (meth) acrylic resin, polystyrene, styrene resin, ABS resin, polycarbonate resin, and the like are more preferable. A thermoplastic resin can be used individually by 1 type or in combination of 2 or more types.

  The adhesive of the present invention is most suitable for bonding an article (resin molded body) made of the same thermoplastic resin as the thermoplastic resin contained in the adhesive. Since the thermoplastic resin contained in the adhesive is a thermoplastic resin that is highly soluble in liquid bromine, when the adhesive of the present invention is applied to the article, at least a part of the surface layer portion on the surface of the article Is dissolved in the coating film made of the adhesive of the present invention. When the coating film is dried in this state, a solidified layer in which the surface layer portion of the article and the coating film are almost uniformly integrated is formed, so that the adhesive strength between the articles can be remarkably increased.

  Examples of the adhesive additive contained in the adhesive of the present invention include leveling agents, fillers (for example, inorganic fine particles such as colloidal silica and alumina sol, organic fine particles such as polymethyl methacrylate, talc, mica, Glass fiber, calcium silicate fiber, potassium titanate fiber, carbon fiber or other fibrous or plate-like inorganic filler), antifoaming agent, sagging inhibitor, wetting and dispersing agent, coupling agent, viscosity modifier, UV absorber , Light stabilizers, crosslinking agents (such as organic peroxides), flame retardants, plasticizers, lubricants, rust inhibitors, fluorescent brighteners, heat absorbers, flame retardants, antistatic agents, dehydrating agents, etc. Can be mentioned. An additive can be used individually by 1 type or in combination of 2 or more types. In addition, the adhesive agent of this invention can be conveniently used also as a coating material by containing various colorants, such as a pigment and dye.

  The adhesive of the present invention includes one article, another article, and an adhesive layer that is interposed between and adheres to each other, and the adhesive layer is formed by drying and solidifying the adhesive of the present invention. It is a solidified layer. Although the thickness of an adhesive layer is not specifically limited, For example, it is set to the range of 1 micrometer-3 mm, Preferably 10 micrometers-50 micrometers.

  Here, the shape of one article and another article is not particularly limited, and the materials constituting them are not particularly limited. Synthetic resin materials such as thermoplastic resins and thermosetting resins, various metal materials, ceramics Examples include materials, wood, and papers. Among these, from the viewpoint of adhesive strength and the like, at least the material constituting the surface layer portion is preferably a synthetic resin material, more preferably a thermoplastic resin, and a thermoplastic that is soluble in liquid bromine or an organic solvent in the adhesive. A resin is more preferable, and a molded body obtained by molding a thermoplastic resin into a sheet or film is particularly preferable. The materials constituting one article and the other article may be the same or different, but the same material is preferable from the viewpoint of adhesive strength and the like. In addition, the contact area between the adhesive and one or other articles is appropriately selected according to the type of thermoplastic resin contained in the adhesive, the material, shape, size, or use of the adhesive of the one or other article. Is done.

  The adhesive of the present invention includes, for example, a step (application step) of applying an adhesive to a predetermined region (adhesion scheduled region) on one article surface, a surface (application surface) on which an adhesive coating film is formed, and the like. A predetermined region (adhesion planned region) of the article, and a step of forming an adhesive layer that is interposed between one article and another article and is in contact with both (adhesion process); And a step of drying and solidifying (drying step).

  Here, as one article and another article, an article having at least a surface layer portion made of a thermoplastic resin (preferably an article that is a molded article of the thermoplastic resin, more preferably a molded article of a thermoplastic resin capable of being liquid bromine. ) Is used, the thermoplastic resin that is interposed between the surface of the one article and the adhesive layer and forms the surface layer of the one article and the thermoplastic resin contained in the adhesive are mixed. A thermoplastic resin that is interposed between the surface (adhesive layer) and / or the surface of the other article and the adhesive layer and constitutes a surface layer of the other article, and a thermoplastic resin contained in the adhesive A second layer (second bonding layer) in which is mixed is formed. Thereby, the adhesiveness of one and other articles | goods and an adhesive layer increases notably, and the adhesive strength of one and other articles | goods improves notably.

  In the application step, the adhesive may be applied not only to the adhesion planned area of one article but also to the adhesion planned area of another article as necessary. As an adhesive application method, any known application method can be employed, for example, a flow coating method, a roll coating method, a spraying method, an airless spray method, an air spray method, a brush coating method, a trowel coating method, a dipping method, Examples thereof include a pulling method, a nozzle method, a winding method, a flow method, a piling method, a patching method, an electrostatic coating method, a bar coder method, a curtain coater method, a curtain flow coating method, an air knife method, a gravure method, and a screen printing method. Among these coating methods, a spraying method, an airless spray method, an air spray method and the like are preferable. Also, the amount of adhesive applied is not particularly limited. For example, the adhesive is applied so that the thickness of the solidified layer of the coating film made of the adhesive is in the range of, for example, 1 μm to 0.5 mm, preferably 10 μm to 30 μm. The coating amount is selected according to the resin concentration in the agent.

  Further, the heating temperature in the drying step is not particularly limited and is appropriately selected according to the content of liquid bromine and organic solvent in the adhesive, the type of organic solvent, etc., for example, in the range of 40 ° C to 130 ° C. Is set. Even when heated to the above temperature range, the flammability of the organic solvent is reduced by the presence of liquid bromine in the adhesive of the present invention, so the risk of ignition is reduced. Moreover, when time may be required, the solidified layer of the adhesive may be formed by natural drying at room temperature.

  Moreover, the liquid resin composition of this invention can be utilized also for manufacture of the fiber reinforced resin molding which integrated the structure containing a fiber, and a thermoplastic resin. That is, the method for producing a fiber-reinforced resin molded body of the present invention includes a step of impregnating or adhering a liquid resin composition to a structure containing fibers, and a step of drying and solidifying the liquid resin composition impregnated in the structure. And including.

  According to the production method of the present invention, the liquid resin composition contains liquid bromine that reduces the flammability of the organic solvent, and since there is less risk of ignition, the liquid resin composition is impregnated or adhered to the fiber structure, By a very simple method of volatilizing a solvent component such as liquid bromine, a fiber reinforced resin molded article in which a thermoplastic resin is impregnated and solidified can be easily produced at a low cost.

  As a structure containing a fiber, the woven fabric and nonwoven fabric which consist of inorganic fiber and / or organic fiber can be used, for example. Examples of the woven fabric include a cloth, a cloth coated or impregnated with a heat resistant resin, and the like. Nonwoven fabrics include wet papermaking, dry papermaking, chemical bonds, resin bonds, thermal bonds, needle punches, spunlaces, stitch bonds, felts, and the like. These are all sheet-like fiber structures, but when a three-dimensional fiber structure is used, a plurality of woven fabrics or nonwoven fabrics described above may be overlapped.

  Examples of the inorganic fiber constituting the fiber structure include rock wool, alumina fiber, silica fiber, silica alumina fiber, glass fiber, milled glass, potassium titanate fiber, aluminum borate fiber, wollastonite (calcium silicate fiber), Examples thereof include calcium carbonate fiber, titanium dioxide fiber, carbon fiber, silicon carbide fiber, silicon nitride fiber, basic magnesium sulfate fiber, zinc oxide fiber, and metal fiber. Examples of the organic fiber include rayon fiber, nylon fiber, polyethylene fiber, polypropylene fiber, polyester fiber, vinylon fiber, aramid fiber, polyvinyl alcohol fiber, and cellulose fiber. The inorganic fiber and organic fiber may be short fibers or long fibers. An inorganic fiber and an organic fiber can be used individually by 1 type or in combination of 2 or more types, respectively.

  According to the method for producing a fiber-reinforced resin molded body of the present invention, a predetermined amount of a liquid resin composition is impregnated or adhered to a fiber structure, and the obtained impregnated body or adhered body is dried at room temperature or heat-dried. Thus, a sheet-like fiber-reinforced resin molded body can be obtained. A plurality of the sheet-like fiber-reinforced resin molded bodies are overlapped and heated under pressure, whereby a fiber-reinforced resin molded body having a three-dimensional shape can be obtained. The heating temperature required for heating and drying may be approximately the same as the temperature at which the adhesive of the present invention is solidified. Here, the amount of the liquid resin composition used can be appropriately selected from a wide range according to the intended use of the fiber-reinforced resin molded article, but preferably, for example, with respect to 100 parts by weight of the fiber structure. 1 to 300 parts by weight, more preferably 5 to 100 parts by weight, still more preferably 45 to 70 parts by weight. Moreover, the heat drying temperature may be in the range of 40 ° C. to 130 ° C. as in the case of the adhesive, or may be room temperature.

  The present invention will be specifically described with reference to examples. In the following, “%” and “part” are based on weight unless otherwise specified. In each of the following examples, ignition did not occur when the liquid resin composition was dried.

Example 1
[Preparation of liquid resin composition]
First, ABS resin and polystyrene resin were dissolved in liquid bromine and thinner in Formulation 1 (part) shown below to obtain Liquid A. Next, the acrylic-modified chlorinated polyolefin resin was dissolved in a part of toluene and cyclohexane to obtain a liquid B. The liquid mixture of A liquid and B liquid was diluted with the remainder of toluene and xylene, and the liquid resin composition of this invention was prepared.

[Formulation 1]
ABS resin (trade name: QF, manufactured by Denki Kagaku Kogyo Co., Ltd.) 2
Polystyrene resin (trade name: MWID, manufactured by Toyo Styrene Co., Ltd.) 0.5
Acrylic modified chlorinated polyolefin resin (trade name: 930S, manufactured by Nippon Paper Industries Co., Ltd.) 5
Liquid bromine 10
Thinner 10
Cyclohexane 2.5
Toluene 43
Xylene 27

(Example 2)
The liquid resin composition of Formula 1 was used as an adhesive. That is, the liquid resin of Formulation 1 on one surface of an ABS resin plate (trade name: Toughace, manufactured by Sumitomo Bakelite Co., Ltd.) having a length of 100 mm, a width of 100 mm, and a thickness of 2 mm so that the thickness after drying and solidification is 5 μm. The composition was applied, the same ABS resin plate as above was bonded to the surface of the obtained coating film, and dried at 40 ° C. for 30 minutes to prepare an ABS resin bonded body. An attempt was made to insert a stainless steel spatula having a thickness of 1.5 mm between the ABS resin plate and the solidified layer to the solidified layer of the obtained bonded body, but it could not be inserted. Further, when the spatula was further pressed, it was found that although the entire bonded body was deformed, no peeling occurred, and the two ABS resin plates were bonded extremely firmly.

(Example 3)
A liquid resin composition of Formulation 2 was obtained in the same manner as in Example 1 except that the ABS resin was changed to a polymethyl methacrylate resin (hereinafter referred to as “PMMA resin”) in the liquid resin composition of Formulation 1. . This liquid resin composition was used as an adhesive. That is, the above liquid resin composition is formed on one surface of a PMMA resin plate (trade name: Acrylite, manufactured by Mitsubishi Rayon Co., Ltd.) having a length of 100 mm, a width of 100 mm, and a thickness of 2 mm so that the thickness after drying and solidification is 5 μm. The same PMMA resin plate as described above was bonded to the surface of the obtained coating film and dried at 40 ° C. for 30 minutes to prepare a PMMA resin bonded body. An attempt was made to insert a stainless steel spatula having a thickness of 1.5 mm between the PMMA resin plate and the solidified layer to the solidified layer of the obtained bonded body, but it could not be inserted. Further, when the spatula was further pressed, it was found that although the entire bonded body was deformed, no peeling occurred, and the two PMMA resin plates were bonded extremely firmly.

(Comparative Example 1)
In the liquid resin composition of Formula 1 above, an ABS resin adhesive was prepared in the same manner as in Example 2 except that liquid bromine was not used and an ABS paint having a thinner compounding amount changed from 10 parts to 20 parts was used. Produced. When a spatula made of stainless steel having a thickness of 1.5 mm was pressed against the solidified layer of the obtained bonded body, the ABS resin plate was peeled around the boundary between the ABS resin plate and the solidified layer.

(Comparative Example 2)
An ABS resin adhesive is used in the same manner as in Example 1 except that a commercially available instant adhesive (trade name: Aron Alpha (trade name), manufactured by Toa Gosei Co., Ltd.) is used in place of the liquid resin composition of Formulation 1. Was made. When a 1.5 mm thick stainless steel spatula was pressed against the solidified layer of the obtained adhesive and the ABS resin plate was peeled off, peeling occurred around the solidified layer, and two ABS resins The plate partially peeled off.

Example 4
Using the liquid resin composition of Formula 1 and a plain-woven E-glass cloth having a thickness of 0.1 mm (product name; # 1031 S640, manufactured by Nitto Boseki Co., Ltd.), a solvent pre-impregnation tank, a liquid resin composition Using an apparatus consisting of an impregnation tank, a pinch roll, and a heating / drying zone having a length of 10 m, supply methyl ethyl ketone to the solvent pre-impregnation tank and supply the liquid resin composition of the above formulation 1 to the liquid resin composition impregnation tank Then, the feed rate of the plain weave E-glass cloth was adjusted to 1 to 1.5 m / min, and the final temperature of the heating / drying zone was kept at 30 to 70 ° C. to produce a fiber reinforced film.

(Example 5)
Instead of plain weave E-glass cloth, a carbon fiber cloth (trade name: Torayca C6373, manufactured by Toray Industries, Inc.) or an aramid fiber cloth (trade name: K-281, manufactured by Kanebo Corporation) is used. Produced a fiber reinforced film in the same manner as in Example 4.

  From the results of Examples 4 and 5, by using the liquid resin composition of the present invention, it is extremely possible to use a heating temperature of 30 to 70 ° C. without melting the thermoplastic resin at a high temperature of about 200 ° C. It is clear that a fiber reinforced film can be obtained by a simple method.

Claims (10)

  A liquid resin composition in which a resin component is dissolved in a solvent component, wherein the solvent component contains liquid bromine and the resin component contains a thermoplastic resin soluble in the liquid bromine.   The liquid resin composition according to claim 1, wherein the solvent component further comprises an organic solvent compatible with the liquid bromine.   The liquid resin composition according to claim 2, comprising 0.1 to 30% by weight of the resin component, 0.5 to 60% by weight of the liquid bromine, and 35 to 95% by weight of the organic solvent.   The thermoplastic resin is at least one selected from the group consisting of polymethyl (meth) acrylate, polystyrene, styrene resin, ABS resin, polycarbonate resin, polyester resin, polyamide resin, polyolefin resin, and modified polyolefin resin. Item 4. The liquid resin composition according to any one of Items 1 to 3.   The organic solvent is at least one selected from the group consisting of aromatic hydrocarbons, alicyclic hydrocarbons, chain saturated hydrocarbons, acetate esters, ketones, and alcohols. The liquid resin composition as described in any one of -4.   One article, another article, and an adhesive layer that is interposed between the one article and the other article to bond them, and the adhesive layer is any one of claims 1 to 5. An adhesive, which is a solidified layer of the liquid resin composition according to Item.   The adhesive according to claim 6, wherein at least a surface layer portion of the one article and the other article is made of the same kind or a different kind of thermoplastic resin.   The first layer intervening between the one article and the adhesive layer, wherein the thermoplastic resin contained in the one article and the thermoplastic resin contained in the adhesive layer are mixed, and / or the other article. The adhesive according to claim 7, further comprising a second layer that is interposed between the adhesive layer and the thermoplastic resin contained in the other article and the thermoplastic resin contained in the adhesive layer. .   The process of apply | coating the liquid resin composition as described in any one of Claims 1-5 to one article | item, and the process of closely adhering another article | item to the surface by which the said liquid resin composition of the said one article | item was apply | coated. And a step of solidifying the liquid resin composition.   A fiber-reinforced resin molded article comprising a step of impregnating or adhering the liquid resin composition according to any one of claims 1 to 5 to a structure containing fibers, and a step of solidifying the liquid resin composition. Manufacturing method.