JP6752549B2 - Integrated structure and unidirectional fiber reinforced resin tape - Google Patents

Description

The present invention relates to an integrated structure formed by welding a unidirectional fiber-reinforced resin tape and a mating material for the lamination using a thermoplastic resin composition, and a method for producing the same. More specifically, the present invention relates to a composite material having excellent bonding strength and mechanical properties and a method for producing the same.

Compositions consisting of reinforcing fibers and resins are widely used in sports equipment applications, aerospace applications, vehicles, ships and other general industrial applications due to their light weight and excellent mechanical properties. In particular, fiber-reinforced thermoplastic resins are easier to melt by heating and solidify by cooling than fiber-reinforced thermosetting resins, so from the viewpoint of cost reduction such as handleability during molding and shortening of cycle time. It is attracting attention.

Further, in recent years, the applications of fiber-reinforced thermoplastic composite materials have been subdivided into various fields, and when applied as a laminated material or a partial reinforcing material, the fiber has excellent mechanical properties in one direction. As sex fibers and matrix resins, there is an increasing demand for resins having high heat resistance, mechanical properties, chemical resistance, dimensional stability, light weight, and flame retardancy, especially polyphenylene sulfide resin.

When the unidirectional fiber-reinforced polyphenylene sulfide resin composition is used in combination with another resin composition, it is necessary to join the two. For bonding between thermoplastic resins (including fiber-reinforced thermoplastic resins), chemical bonding with an adhesive or a solvent and physical bonding such as heat welding are used. Chemical bonding does not require large equipment, but has problems such as drying and curing time and evaporation of organic solvent. On the other hand, physical bonding is widely used because it has a short bonding time and is suitable for mass production. In recent years, the demand for joint strength has increased due to the increase in size and complexity of parts, and a method of increasing the welding strength in physical bonding, that is, welding has attracted attention.

In order to improve the welding strength, there are methods such as reducing the proportion of the reinforcing fibers contained, or reducing the fluidity of the resin by using a high molecular weight polyphenylene sulfide resin, but the proportion of the reinforcing fibers is reduced. If the mechanical properties of the fiber-reinforced resin composition itself are lowered and the fluidity of the resin is lowered, there is a problem that the productivity in the production of the unidirectional fiber-reinforced polyphenylene sulfide resin composition is lowered.

In Patent Document 1, the welding strength of nylon resin is improved by the formulation of the resin, but the formulation is limited to nylon resin, and other resins are not mentioned.

In Patent Document 2, although the welding strength of the polyamide resin is improved by increasing the viscosity, it is narrowed down to the polyamide resin, and there is a risk that the productivity may decrease due to the decrease in fluidity.

In Patent Document 3, the temperature rises above the melting point. Although the surface layer of the resin composition is changed to one suitable for welding to improve the welding strength, it is necessary to keep the mold and the like at a high temperature, and there remains a problem in energy cost.

Japanese Unexamined Patent Publication No. 2001-11307 JP-A-2007-92004 Japanese Unexamined Patent Publication No. 2005-131902

The present invention relates to the above-mentioned prior art, and an object of the present invention is to improve the welding strength at the time of welding of a laminated plate in which a unidirectional fiber reinforced resin tape is laminated, thereby integrating excellent mechanical properties and surface appearance. To provide the structure.

As a result of diligent studies to solve the above problems, the present inventors have found an integrated structure using the following unidirectional fiber reinforced resin tape.
(1) (I) A laminated board in which a unidirectional fiber reinforced resin tape in which reinforcing fibers are aligned in one direction is laminated, and (II) a mating material of the laminated body using a thermoplastic resin composition are welded. The unidirectional fiber reinforced resin tape (I) unidirectionally aligns the reinforcing fibers surface-treated with a sizing agent composed of a polyfunctional compound containing chlorine in the polymer chain in one direction. A unidirectional fiber-reinforced resin tape impregnated with a polyphenylene sulfide resin as a resin, and the amount of the sizing agent attached to the reinforcing fibers surface-treated with a sizing agent composed of a polyfunctional compound containing chlorine in the polymer chain. 0.2 to 2% by mass, the chlorine in the sizing agent is 3 to 15% by mass, and the polyphenylene sulfide resin contains 30 to 250 ppm of inorganic chlorine. ..
(2) The integrated structure according to (1), wherein the reinforcing fibers occupy 20 to 70% by mass of the unidirectional fiber reinforced resin tape (I).
( 3 ) The integrated structure according to (1) or (2) , wherein the sizing agent is made of an aliphatic epoxy resin.
( 4 ) The matrix resin impregnated in the unidirectional fiber reinforced resin tape arranged at least on the outermost surface layer of the laminated board has a molecular weight of 50,000 or more and less than 100,000 (1) to The integrated structure according to ( 3 ).
( 5 ) The integrated structure according to any one of (1) to ( 4 ), wherein the thermoplastic resin composition (II) is a polyphenylene sulfide resin composition.
(6) A unidirectional fiber reinforced resin tape in which reinforcing fibers surface-treated with a sizing agent composed of a polyfunctional compound containing chlorine in a polymer chain are aligned in one direction and impregnated with a polyphenylene sulfide resin as a matrix resin. The amount of the sizing agent adhered to the reinforcing fibers surface-treated with the sizing agent composed of a polyfunctional compound containing chlorine in the polymer chain is 0.2 to 2% by mass, and the chlorine in the sizing agent is 3-15 as well as a mass%, one-way fiber reinforced resin tape the polyphenylene sulfide resin is characterized by containing 30~250ppm inorganic chlorine.
( 7 ) The unidirectional fiber reinforced resin tape according to (6), wherein the sizing agent is made of an aliphatic epoxy resin.

According to the present invention, the welding strength at the time of welding of a laminated plate in which a unidirectional fibrous reinforcing resin tape is laminated is good, and the integral body has excellent mechanical properties such as tensile strength and flexural rigidity, surface appearance, and durability. A chemical structure can be provided.

It is a schematic schematic diagram of the test body for evaluating the joint strength of the integrated structure which concerns on this invention. It is a schematic cross-sectional view of the manufacturing apparatus of the unidirectional fiber reinforced resin tape used in this invention.

The present invention is an integrated structure obtained by welding (I) a laminated board on which a unidirectional fiber reinforced resin tape is laminated and (II) a mating material of the laminated body using a thermoplastic resin composition. is there. The (I) unidirectional fiber reinforced resin tape comprises reinforcing fibers surface-treated with a sizing agent composed of a polyfunctional compound containing a halogen in the polymer chain.

In the present invention, the (I) unidirectional fiber reinforced resin tape is a reinforced fiber surface-treated with a sizing agent composed of a polyfunctional compound containing halogen in the polymer chain in a polyphenylene sulfide resin as a matrix resin. , A base material contained in a state where the fiber directions are arranged in one direction. The reinforcing fibers surface-treated with a sizing agent composed of a polyfunctional compound containing halogen in the polymer chain are substantially uniformly dispersed in the unidirectional fiber reinforced resin tape 100 without being solidified at a specific position, and are heavy. The reinforcing fibers surface-treated with a sizing agent composed of a polyfunctional compound containing halogen in the coalesced chain are filled with a matrix resin. That is, the reinforcing fibers surface-treated with a sizing agent composed of a polyfunctional compound containing halogen in the polymer chain are impregnated with the matrix resin. A thin-walled unidirectional fiber-reinforced resin tape 100 is manufactured by continuous molding such as a pultrusion molding method.

The proportion of the reinforcing fibers in the unidirectional fiber reinforced resin tape of the present invention is 20 to 70% by mass, preferably 40 to 65% by mass, and more preferably 50 to 65% by mass. When the reinforcing fiber content is 20% by mass or more, the mechanical properties of the obtained molded product are excellent, the reinforcing fiber is excellently reinforced with other base materials, and when the reinforcing fiber content is 70% by mass or less, the matrix resin is excellently impregnated into the reinforcing fiber bundle.

Further, these, a polyphenylene sulfide resin is 30 to 80 wt%, preferably 35 to 60 mass%, more preferably 35 to 50 wt%. When the polyphenylene sulfide resin is 30% by mass or more, the adhesiveness to other base materials is excellent, and when the polyphenylene sulfide resin is 80% by mass or less, the entrainment of air bubbles in the matrix resin of the molded unidirectional fiber reinforced resin tape can be reduced.

The reinforcing fibers used in the present invention are not particularly limited, and examples thereof include carbon fibers, metal fibers, organic fibers, and inorganic fibers.

Examples of the carbon fibers include polyacrylonitrile (PAN) -based carbon fibers, pitch-based carbon fibers, cellulose-based carbon fibers, vapor-phase growth-based carbon fibers, and graphitized fibers thereof. Of these, the PAN-based carbon fiber is a carbon fiber made from polyacrylonitrile fiber. Pitch-based carbon fibers are carbon fibers made from petroleum tar or petroleum pitch. Cellulose-based carbon fibers are carbon fibers made from viscose rayon, cellulose acetate, or the like. The vapor phase growth type carbon fiber is a carbon fiber made from a hydrocarbon or the like. Among these carbon fibers, PAN-based carbon fibers are preferably used because they have an excellent balance between strength and elastic modulus.

Examples of the metal fiber include fibers made of a metal such as iron, gold, silver, copper, aluminum, brass, and stainless steel.

Examples of the organic fiber include fibers made of an organic material such as aramid fiber, polyphenylene sulfide fiber, polyester fiber, polyamide fiber, and polyethylene fiber. Examples of aramid fibers include para-aramid fibers having excellent strength and elastic modulus and meta-aramid fibers having excellent flame retardancy and long-term heat resistance. Examples of the para-aramid fiber include polyparaphenylene terephthalamide fiber and copolyparaphenylene-3,4'-oxydiphenylene terephthalamide fiber, and examples of the meta-type aramid fiber include polymetaphenylene isophthalamide fiber. Can be mentioned. As the aramid fiber, a para-aramid fiber having a higher elastic modulus than the meta-aramid fiber is preferably used.

Examples of the inorganic fiber include fibers made of an inorganic material such as glass, basalt, silicon carbide, and silicon nitride. Examples of the glass fiber include E glass fiber (for electricity), C glass fiber (for corrosion resistance), S glass fiber, and T glass fiber (high strength and high elastic modulus), and any of these may be used. Basalt fiber is a fiber of basalt, which is a mineral, and has extremely high heat resistance. Basalt generally contains 9 to 25% of FeO or FeO ₂ which is an iron compound and 1 to 6% of TiO or TiO ₂ which is a titanium compound, but these components are increased in a molten state to become fibrous. It is also possible to do.

In the present invention, it is more preferable to use at least one reinforcing fiber selected from carbon fiber, glass fiber, basalt fiber or aramid fiber as the reinforcing fiber, and among these, mechanical properties such as weight reduction and strength are exhibited. It is particularly preferable to use carbon fibers that exhibit efficiently.

A plurality of types of reinforcing fibers may be used in combination, and a complex effect can be expected by combining these fibers. For example, by combining carbon fiber and glass fiber, a high reinforcing effect and low cost by carbon fiber can be expected. It is possible to reduce costs by using simple glass fiber.

In a unidirectional fiber reinforced resin tape, the reinforcing fiber is usually composed of one or a plurality of reinforcing fiber bundles in which a large number of single fibers are bundled. The total number of filaments (number of single fibers) of the reinforcing fibers when one or a plurality of reinforcing fiber bundles are arranged is preferably in the range of 1,000 to 2,000,000. From the viewpoint of productivity, the total number of filaments of the reinforcing fibers is more preferably 1,000 to 1,000,000, further preferably 1,000 to 600,000, and 1,000 to 300,000. Especially preferable. The upper limit of the total number of filaments of the reinforcing fibers may be such that productivity, dispersibility, and handleability can be kept good in consideration of the balance between dispersibility and handleability.

One reinforcing fiber bundle is formed by bundling 1,000 to 50,000 single fibers of reinforcing fibers having an average diameter of 5 to 10 μm. The average diameter of the single fibers is more preferably 6 to 8 μm. It is preferable to use a reinforcing fiber having a tensile strength of 3,000 to 6,000 MPa. The relationship is that the strength of the reinforcing fiber (MPa) = (strength of single fiber (N)) / cross-sectional area of single fiber (mm ² ).

Next, a sizing agent composed of a polyfunctional compound containing a halogen in the polymer chain, which is attached to the surface of the reinforcing fiber, will be described.

The amount of the sizing agent adhered to the reinforcing fibers surface-treated with the sizing agent composed of a polyfunctional compound containing a halogen in the polymer chain used in the present invention is important to be 0.2 to 2% by mass. It is preferably 0.3 to 1.5% by mass, and more preferably 0.3 to 1% by mass or less.

When the amount of the sizing agent adhered to the reinforcing fibers surface-treated with the sizing agent composed of a polyfunctional compound containing halogen in the polymer chain is 0.2% by mass or more, the adhesiveness improving effect appears, and when it is 2% by mass or less. , Does not deteriorate the physical properties of the matrix resin.

By surface-treating the reinforcing fibers using a polyfunctional compound as a sizing agent, even if the amount added is small, it is effectively adapted to the surface characteristics such as functional groups on the surface of the reinforcing fibers to improve the adhesiveness and the overall composite characteristics. Can be made to. In addition, the focusing property, bending resistance and scratch resistance are improved, and the occurrence of fluff and thread breakage is suppressed in the high-order processing process, and the high-order workability can be improved as a so-called glue or focusing agent. it can.

In addition, as the sizing agent, other components such as bisphenol type epoxy compound, linear low molecular weight epoxy compound, polyethylene glycol, polyurethane, polyester, emulsifier or surfactant are added to adjust the viscosity, improve scratch resistance, and improve fluff resistance. It may be added for the purpose of improving the focusing property and the higher workability.

The means for applying the sizing agent is not particularly limited, and examples thereof include a method of immersing the sizing agent in the sizing liquid via a roller, a method of contacting the roller with the sizing liquid attached, and a method of atomizing the sizing liquid and spraying it. .. Further, either a batch type or a continuous type may be used, but a continuous type having good productivity and small variation is preferable. At this time, it is preferable to control the sizing liquid concentration, temperature, thread tension, etc. so that the amount of the sizing agent active ingredient adhered to the reinforcing fibers is uniformly within an appropriate range. Further, it is more preferable to ultrasonically vibrate the reinforcing fibers when the sizing agent is applied.

The drying temperature and drying time should be adjusted according to the amount of the compound attached, but the solvent used to apply the sizing agent is completely removed, the time required for drying is shortened, while the thermal deterioration of the sizing agent is prevented and the sizing is performed. From the viewpoint of preventing the reinforcing fiber bundle formed of the reinforcing fibers surface-treated with the agent from becoming hard and deteriorating the spreadability of the bundle, the drying temperature is preferably 150 ° C. or higher and 350 ° C. or lower. , 180 ° C. or higher and 250 ° C. or lower is more preferable.

Examples of the solvent used for the sizing agent include water, methanol, ethanol, dimethylformamide, dimethylacetamide, acetone and the like, but water is preferable from the viewpoint of easy handling and disaster prevention. Therefore, when a compound that is insoluble or sparingly soluble in water is used as a sizing agent, it is preferable to add an emulsifier and a surfactant and disperse the compound in water. Specifically, as emulsifiers and surfactants, styrene-maleic anhydride copolymers, olefin-maleic anhydride copolymers, formalin condensates of naphthalene sulfonate, anionic emulsifiers such as sodium polyacrylic acid, etc. Cationic emulsifiers such as polyethyleneimine and polyvinylimidazolin, nonylphenolethylene oxide adducts, polyvinyl alcohol, polyoxyethylene ether ester copolymers, nonionic emulsifiers such as sorbitan ester ethyloxide adducts and the like can be used, but interactions can be used. A nonionic emulsifier with a small amount is preferable because it does not hinder the adhesive effect of the polyfunctional compound.

Next, a polyfunctional compound having a halogen in the polymer chain used in the present invention will be described. The polyfunctional compound used in the present invention is not particularly limited, but a compound having two or more functional groups such as an epoxy group, a urethane group, an amino group, and a carboxyl group in one molecule can be used, and these may be one or two. Seeds or more may be used together. If the number of functional groups is less than two, the adhesiveness between the reinforcing fiber and the matrix resin cannot be sufficiently exhibited. Therefore, it is essential that the number of functional groups is 2 or more, and more preferably 3 or more.

It is important that the proportion of the amount of halogen in the sizing agent composed of the polyfunctional compound containing halogen in the polymer chain used in the present invention is 3 to 15% by mass. It is preferably 5 to 13% by mass, more preferably 5.5 to 12% by mass.

It is considered that the presence of halogen contained in the polymer chain improves the electrical affinity between the sizing agent and the reinforcing fiber, and between the sizing agent and the matrix resin, so that the adhesive strength at the composite material interface is improved, and as a result, the adhesive strength is improved. , The strength of the unidirectional fiber reinforced resin tape can be improved.

When the ratio of the amount of halogen in the sizing agent composed of the polyfunctional compound containing halogen in the polymer chain is 3% by mass or more, the electrical affinity between the sizing agent and the reinforcing fiber and between the sizing agent and the matrix resin is improved. , 15% by mass or less, it becomes difficult to inhibit the reaction between the functional group other than the halogen in the polyfunctional compound and the reinforcing fiber or the matrix resin.

The halogen in the sizing agent composed of a polyfunctional compound containing halogen in the polymer chain used in the present invention is not particularly limited, but chlorine, fluorine, bromine and the like can be used. Among them, chlorine is particularly preferable. Since the polyphenylene sulfide resin described later can contain a small amount of chlorine in the manufacturing process, when chlorine is used as the halogen in the sizing agent, the affinity with chlorine in the polyphenylene sulfide resin can be increased.

Specific compounds of the polyfunctional compound used as a sizing agent composed of a polyfunctional compound containing halogen in the polymer chain include a polyfunctional epoxy resin, and examples of the polyfunctional epoxy resin include bisphenol A type epoxy resin and bisphenol. Examples thereof include F-type epoxy resin, aliphatic epoxy resin, and phenol novolac type epoxy resin. Of these, an aliphatic epoxy resin that easily exhibits adhesiveness to the matrix resin is preferable. Normally, when an epoxy resin has a large number of epoxy groups, the cross-linking density after the cross-linking reaction becomes high, so that the structure tends to have low toughness, and even if it is present between the reinforcing fiber and the matrix resin, it is brittle. It is easy to peel off and the strength of the fiber reinforced composite material may not be exhibited. On the other hand, since the aliphatic epoxy resin has a flexible skeleton, it tends to have a structure having high toughness even if the crosslink density is high. When it is present between the reinforcing fiber and the matrix resin, it is preferable because it is flexible and difficult to peel off, so that the strength of the fiber-reinforced composite material can be easily improved.

Specific examples of the aliphatic epoxy resin include, for example, in the diglycidyl ether compound, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ethers, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ethers, 1,4- Examples thereof include butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether, polyalkylene glycol diglycidyl ether and the like. Among the polyglycidyl ether compounds, glycerol polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol polyglycidyl ethers, sorbitol polyglycidyl ethers, arabitol polyglycidyl ethers, trimethylolpropane polyglycidyl ethers, trimethylolpropane Examples thereof include glycidyl ethers, pentaerythritol polyglycidyl ethers, and polyglycidyl ethers of aliphatic polyhydric alcohols.

Among the aliphatic epoxy resins, an aliphatic polyglycidyl ether compound having a large number of highly reactive glycidyl groups is preferable. Of these, glycerol polyglycidyl ether, diglycerol polyglycidyl ether, polyethylene glycol glycidyl ethers, and polypropylene glycol glycidyl ethers are more preferable. The aliphatic polyglycidyl ether compound is preferable because it has a good balance of flexibility, crosslink density, and compatibility with the matrix resin, and it is easy to effectively improve the adhesiveness.

Next, the polyphenylene sulfide resin used as the matrix resin in the present invention will be described.

The polyphenylene sulfide resin used in the present invention is not particularly limited, and examples of the polymer type include a crosslinked type, a linear type, and a semi-crosslinked type, which are resins having a structure composed of benzene and sulfur. ..

The method for producing the polyphenylene sulfide resin is also not particularly limited, and for example, a flash method polyphenylene sulfide resin, a quench method polyphenylene sulfide resin, or a mixture thereof can be used.

In the flash method, the polymerization reaction product is flushed from a high temperature and high pressure (usually 250 ° C. or higher, 8 kg / cm ² or higher) into an atmosphere of normal pressure or reduced pressure, and the polymer is recovered in powder form at the same time as the solvent is recovered. A method, where flash means ejecting a polymerization reactant from a nozzle. Specifically, for example, nitrogen or water vapor under normal pressure is raised as the flashing atmosphere, and the temperature is usually selected in the range of 150 ° C. to 250 ° C.

On the other hand, the quench method is a method in which the polymerization reaction product is gradually cooled while being crystallized, and then the solid material is filtered and recovered.

Further, it is also possible to add a cross-linking agent such as a peroxide and heat in an oxygen atmosphere after the completion of the polymerization to increase the molecular weight by a cross-linking treatment by superheating.

Furthermore, it is also possible to perform a dry heat treatment for the purpose of suppressing thermal oxidation cross-linking and removing volatilization.

The shape of the polyphenylene sulfide resin is not particularly limited. If the shape is granular or powdery, it may be supplied to the feeder as it is as a matrix resin. Further, it may be used after being formed into flakes or pellets.

It is important that the polyphenylene sulfide resin used in the present invention has 30 to 250 ppm of inorganic chlorine. It is preferably 40 to 200 ppm, more preferably 40 to 150 ppm.

The presence of inorganic chlorine in the polyphenylene sulfide resin is thought to improve the electrical affinity between the sizing agent and the reinforcing fibers, and between the sizing agent and the matrix resin, thus improving the adhesive strength at the composite interface, resulting in improved adhesive strength. The strength of the unidirectional fiber reinforced resin tape can be improved.

Further, this inorganic chlorine has a high affinity with halogen in a polyfunctional compound containing halogen in the polymer chain, and has an amount of inorganic chlorine in the above range in the polyphenylene sulfide resin, so that electricity between the sizing agent and the matrix resin can be obtained. It is considered that the affinity for plastics is further improved.

When the inorganic chlorine content of the polyphenylene sulfide resin is 30 ppm or more, the effect of improving the adhesiveness appears, and when it is 250 ppm or less, the physical properties of the matrix resin are not deteriorated.

Further, the polyphenylene sulfide resin may contain other fillers and additives as long as the object of the present invention is not impaired. Examples of these are inorganic fillers, flame retardants, conductivity-imparting agents, crystal nucleating agents, UV absorbers, antioxidants, vibration damping agents, antibacterial agents, insect repellents, deodorants, anticoloring agents, heat stabilizers. , Release agent, antistatic agent, plasticizer, lubricant, colorant, pigment, dye, foaming agent, antifoaming agent, or coupling agent.

(I) The thermoplastic resin composition, which is the mating material of the laminated board in which the unidirectional fiber reinforced resin tape is laminated, is not particularly limited, but is used as the matrix resin of the unidirectional fiber reinforced resin tape. It is preferable to use a thermoplastic resin that can be easily bonded to the polyphenylene sulfide resin and can exhibit the bonding strength. In particular, when the same polyphenylene sulfide resin as the matrix resin of the (I) unidirectional fiber reinforced resin tape is used as the (II) thermoplastic resin composition, warpage, sink marks, etc. due to the difference in heat shrinkage even during cooling after joining are used. Is less likely to occur, and high bonding strength can be exhibited.

The (II) thermoplastic resin composition is preferably a fiber-reinforced resin composition containing a fibrous reinforcing material. The reinforcing fiber used as the fibrous reinforcing material is not particularly limited, but carbon fiber, metal fiber, organic fiber, and inorganic fiber can be preferably used.

The molecular weight of the resin used for the (I) unidirectional fiber reinforced resin tape used for at least 1 ly of the surface layer of the laminated board on which the (I) unidirectional fiber reinforced resin tape in the present invention is laminated is 50,000 or more and less than 100,000. Is preferable. It is more preferably 60,000 or more and less than 80,000, and further preferably 65,000 or more and less than 70,000.

In a laminated board of a unidirectional fiber reinforced polyphenylene sulfide resin composition, the welding strength is improved when the molecular weight of the matrix resin in the adhesive portion arranged on the outermost layer is 50,000 or more, and the fluidity is low when the molecular weight is 100,000 or less. , Does not reduce the productivity of unidirectional fiber reinforced resin tape.

In the present invention, the molecular weight of the resin used for the unidirectional fiber reinforced resin tape can be measured by a known method.

In the integrated structure according to the present invention, as the form of the welding, at least one selected from the group consisting of vibration welding, hot plate welding, ultrasonic welding, dielectric heating welding, induced superheat welding and laser heating welding is selected. It can be preferably adopted.

Next, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

(1) Method for measuring reinforcing fiber mass content (%) and matrix resin mass content (%) After weighing about 0.5 g of unidirectional fiber reinforced resin tape (W1) (reading to the 4th place in the minority) , The matrix resin is completely thermally decomposed by leaving it in an electric furnace (capacity 120 cm ³ ) set to a temperature of 500 ° C. for 30 minutes in a nitrogen stream of 50 ml / min. Then, it was transferred to a container in a dry nitrogen stream of 20 liters / minute, cooled for 15 minutes, and then the reinforcing fiber bundle was weighed (W2) (read to the fourth decimal place) to determine the amount of the reinforcing fiber bundle. Next, each value was calculated from each measured value by the following formula (rounded to the first decimal place). The measurement was performed twice, and the average value was taken as each mass content.
Reinforcing fiber mass content (%) = W2 / W1
Matrix resin mass content (%) = 100-Reinforced fiber mass content (%)

(2) Method for measuring the mass content (%) of the sizing agent composed of a polyfunctional compound containing a halogen in the polymer chain After weighing (W3) (reading up to the 4th position in the minority) of about 2 g of the sizing agent-attached carbon fiber bundle. , In a nitrogen stream of 50 ml / min, leave it in an electric furnace (capacity 120 cm ³ ) set at a temperature of 450 ° C. for 15 minutes to completely pyrolyze the sizing agent. Then, the carbon fiber bundle is transferred to a container in a dry nitrogen stream of 20 liters / minute, cooled for 15 minutes, weighed (W4) (read to the third decimal place), and the amount of sizing agent adhered by W3-W4 is measured. I asked. Next, the amount of sizing agent adhered was calculated from each measured value by the following formula (rounded to the first decimal place). The measurement was performed twice, and the average value was taken as the mass content of the sizing agent.
Sizing agent mass content (%) = (W3-W4) / W3

(3) Method for measuring the inorganic chlorine content (ppm) in the polyphenylene sulfide resin After weighing about 1 g of the polyphenylene sulfide resin (W5) (reading to the fourth decimal place), put it in an Erlenmeyer flask containing 100 ml of ultrapure water. It was put in and sealed, and shaken at 60 ° C. for 24 hours to elute. The obtained eluate was filtered, and chloride ions were measured by an ion chromatograph method in accordance with JIS K 0102.35.3 (2013). The chloride content of the eluate obtained by the ion chromatograph method was defined as Amg / g, and the inorganic chlorine content in the polyphenylene sulfide resin was calculated by the following formula (rounded to the first decimal place). The measurement was performed twice, and the average value was taken as the inorganic chlorine content in the polyphenylene sulfide resin.
Inorganic chlorine content (ppm) = A / (10 x W5)

(4) Melt flow rate measurement method A melt indexer (manufactured by Toyo Seiki Co., Ltd.) is used for measurement, and an orifice with a hole diameter of 2.096 mm and a length of 8.00 mm is used at a temperature of 315.5 ° C. and a load of 5000 g. The measurement was performed under the conditions. About 7 g of the sample was put into the apparatus, and after 1 minute, the piston was inserted, and after another 4 minutes, a load was applied to the piston and measurement was performed.

(5) Tensile test The joint strength (tensile strength) at the joint portion of the above-mentioned laminated board was measured by a lap shear test (shear test) (JIS K6851 (1994)) as shown in FIG. In the test method shown in FIG. 1, (I) the laminated plate 11 of the unidirectional fiber-reinforced resin tape and (II) the thermoplastic resin composition 12 are joined and integrated by welding at the joint portion 13, and (I) one direction. The end of the laminated plate 11 of the sex fiber reinforced resin tape and the end of (II) the thermoplastic resin composition 12 are gripped by the chuck portions 14 and 15 of the tensile tester, and a shear load is applied to the joint portion 13 by the tensile tester. In addition, (I) the laminated plate 11 of the unidirectional fiber-reinforced resin tape and (II) the thermoplastic resin composition 12 are pulled in opposite directions, and the joint portion 13 is broken or deformed by a predetermined amount or more (for example, interfacial breakage). The joint strength was quantitatively measured by measuring the tensile strength at the time of occurrence. The wrap allowance (bonding allowance) of (I) the laminated plate 11 of the unidirectional fiber reinforced resin tape and (II) the thermoplastic resin composition 12 is 12.5 mm, the length of each test piece is 100 mm, the width is 25 mm, and the thickness. It was 2 mm and the length of each chuck portion was 37.5 mm.
The strength was judged according to the following criteria, and AA to B were accepted.
AA: Tensile strength 30 MPa or more A: Tensile strength 25 MPa or more and less than 30 MPa B: Tensile strength 20 MPa or more and less than 25 MPa C: Tensile strength 15 MPa or more and less than 20 MPa D: Less than 15 MPa

(6) Reinforcing fiber (a) Reinforcing fiber surface-treated with a sizing agent composed of a polyfunctional compound containing halogen in the polymer chain (A) Sizing agent composed of a polyfunctional compound containing halogen in the polymer chain (a-1) : Polyethylene glycol diglycidyl ether (EX832 manufactured by Nagase ChemteX Corporation), chlorine concentration 7.3% by mass
(A-2): Polyglycerol polyglycidyl ether (EX512 manufactured by Nagase ChemteX Corporation), chlorine concentration 6.5% by mass
(A-3): Sorbitol polyglycidyl ether (EX614B manufactured by Nagase ChemteX Corporation), chlorine concentration 10.1% by mass
(A-4): Polyethylene glycol diglycidyl ether (EX841 manufactured by Nagase ChemteX Corporation), chlorine concentration 1.9% by mass
(A-5): Sorbitol polyglycidyl ether (EX614B manufactured by Nagase ChemteX Corporation), chlorine concentration 19.4% by mass
(B) Reinforcing Fiber Acrylonitrile-based polymer was spun and fired to obtain carbon fibers having a total number of filaments of 12,000, a total fineness of 800 tex, a strand tensile strength of 5 GPa, and a strand tensile elastic modulus of 230 GPa. Next, the carbon fibers were electrolyzed to obtain carbon fibers as a raw material.

(B) Polyphenylene sulfide resin (B-1) Polyphenylene sulfide resin (inorganic chlorine concentration 100 ppm, molecular weight 43,000)
In an autoclave with a stirrer, 9.35 kg (80 mol) of 48% sodium hydrosulfide, 7.03 kg (83.6 mol) of 48% sodium hydroxide, 13.0 kg (131 mol) of N-methyl-2-pyrrolidone (NMP). , 1.07 kg (6.51 mol) of 50% sodium acetate aqueous solution was charged, and gradually heated to 235 ° C. over about 3 hours while passing nitrogen under normal pressure, 8.35 kg of water and 0.17 kg (1.7 mol) of NMP. ) Was distilled off, and then the reaction vessel was cooled to 160 ° C. During this operation, hydrogen sulfide was scattered outside the 1.6 mol system.

Next, 11.9 kg (81.0 mol) of p-dichlorobenzene (p-DCB) and 10.5 kg (106 mol) of NMP were additionally added, and the reaction vessel was sealed under nitrogen gas. The temperature was raised from 200 ° C. to 270 ° C. at a rate of 0.6 ° C./min with stirring at 240 rpm, and the reaction was continued at 270 ° C. for 140 minutes. Then, while cooling to 240 ° C. over 20 minutes, 2.82 kg (157 mol) of water was injected into the system, and then cooled from 240 ° C. to 210 ° C. at a rate of 0.4 ° C./min. After that, it was rapidly cooled to near room temperature.

The contents were taken out, diluted with about 33 liters of NMP, stirred at 85 ° C. for 30 minutes, and the solids were filtered off by sieving (80 mesh). The obtained solid content was similarly diluted with about 40 liters of NMP, stirred and filtered. Then, the mixture was diluted with 70 liters of warm water, stirred at 70 ° C. for 30 minutes, and then filtered through an 80 mesh wire mesh to recover the solid content, which was repeated a total of 3 times. The obtained solid content and 28 g of acetic acid were diluted with 70 liters of warm water, stirred at 70 ° C. for 30 minutes, and then filtered through an 80 mesh wire mesh to recover the solid content. Further, the solid content was diluted with 70 liters of warm water, stirred at 70 ° C. for 30 minutes, and then filtered through an 80 mesh wire mesh to recover the solid content. The solid content thus obtained was dried at 120 ° C. under a nitrogen stream to obtain a dried PPS. The melt flow rate of the obtained PPS was about 600 g / 10 minutes, and the inorganic chlorine content was 100 ppm.

(B-2) Polyphenylene sulfide resin (inorganic chlorine concentration 720 ppm, molecular weight 67,000)
In an autoclave with a stirrer, 9.35 kg (80 mol) of 48% sodium hydrosulfide, 6.92 kg (82.4 mol) of 48% sodium hydroxide, 13.0 kg (131 mol) of N-methyl-2-pyrrolidone (NMP). , 5.02 kg (30.6 mol) of 50% sodium acetate aqueous solution was charged, and gradually heated to 235 ° C. over about 3 hours while passing nitrogen under normal pressure, and 9.93 kg of water and 0.20 kg (2.0 mol) of NMP. ) Was distilled off, and then the reaction vessel was cooled to 160 ° C. During this operation, hydrogen sulfide was scattered outside the 1.6 mol system.

Next, 11.8 kg (80.2 mol) of p-dichlorobenzene (p-DCB) and 10.5 kg (106 mol) of NMP were additionally added, and the reaction vessel was sealed under nitrogen gas. The temperature was raised from 200 ° C. to 235 ° C. at a rate of 0.8 ° C./min with stirring at 240 rpm, and the reaction was carried out at 235 ° C. for 40 minutes. The temperature was then raised to 270 ° C. at a rate of 0.8 ° C./min and the reaction was continued at 270 ° C. for 70 minutes. Then, 2.68 kg (149 mol) of water was injected into the system while cooling to 240 ° C. over 20 minutes, and then cooled from 240 ° C. to 210 ° C. at a rate of 0.4 ° C./min. After that, it was rapidly cooled to near room temperature.

The contents were taken out, diluted with about 33 liters of NMP, stirred at 85 ° C. for 30 minutes, and the solids were filtered off by sieving (80 mesh). The obtained solid content was similarly diluted with about 40 liters of NMP, stirred and filtered. Then, the mixture was diluted with 70 liters of warm water, stirred at 70 ° C. for 30 minutes, and then filtered through an 80 mesh wire mesh to recover the solid content, which was repeated a total of 3 times. The obtained solid content and 28 g of acetic acid were diluted with 70 liters of warm water, stirred at 70 ° C. for 30 minutes, and then filtered through an 80 mesh wire mesh to recover the solid content. Further, the solid content was diluted with 70 liters of warm water, stirred at 70 ° C. for 30 minutes, and then filtered through an 80 mesh wire mesh to recover the solid content. The solid content thus obtained was dried at 120 ° C. under a nitrogen stream to obtain a dried PPS. The melt flow rate of the obtained PPS was about 105 g / 10 minutes, and the chlorine content was 720 ppm.

(B-3) Polyphenylene sulfide resin (inorganic chlorine concentration 20 ppm, molecular weight 43,000)
In an autoclave with a stirrer, 9.35 kg (80 mol) of 48% sodium hydrosulfide, 7.03 kg (83.6 mol) of 48% sodium hydroxide, 13.0 kg (131 mol) of N-methyl-2-pyrrolidone (NMP). , 1.07 kg (6.51 mol) of 50% sodium acetate aqueous solution was charged, and gradually heated to 235 ° C. over about 3 hours while passing nitrogen under normal pressure, 8.35 kg of water and 0.17 kg (1.7 mol) of NMP. ) Was distilled off, and then the reaction vessel was cooled to 160 ° C. During this operation, hydrogen sulfide was scattered outside the 1.6 mol system.

Next, 11.9 kg (81.0 mol) of p-dichlorobenzene (p-DCB) and 10.5 kg (106 mol) of NMP were additionally added, and the reaction vessel was sealed under nitrogen gas. The temperature was raised from 200 ° C. to 270 ° C. at a rate of 0.6 ° C./min with stirring at 240 rpm, and the reaction was continued at 270 ° C. for 140 minutes. Then, while cooling to 240 ° C. over 20 minutes, 2.82 kg (157 mol) of water was injected into the system, and then cooled from 240 ° C. to 210 ° C. at a rate of 0.4 ° C./min. After that, it was rapidly cooled to near room temperature.

The contents were taken out, diluted with about 33 liters of NMP, stirred at 85 ° C. for 30 minutes, and the solids were filtered off by sieving (80 mesh). The obtained solid content was similarly diluted with about 40 liters of NMP, stirred and filtered. Then, the mixture was diluted with 70 liters of warm water, stirred at 70 ° C. for 30 minutes, and then filtered through an 80 mesh wire mesh to recover the solid content, which was repeated 6 times in total. The obtained solid content and 28 g of acetic acid were diluted with 70 liters of warm water, stirred at 70 ° C. for 30 minutes, and then filtered through an 80 mesh wire mesh to recover the solid content. Further, the solid content was diluted with 70 liters of warm water, stirred at 70 ° C. for 30 minutes, and then filtered through an 80 mesh wire mesh to recover the solid content. The solid content thus obtained was dried at 120 ° C. under a nitrogen stream to obtain a dried PPS. The melt flow rate of the obtained PPS was about 600 g / 10 minutes, and the inorganic chlorine content was 20 ppm.

(B-4) Polyphenylene sulfide resin (inorganic chlorine concentration 300 ppm, molecular weight 43,000)
In an autoclave with a stirrer, 9.35 kg (80 mol) of 48% sodium hydrosulfide, 7.03 kg (83.6 mol) of 48% sodium hydroxide, 13.0 kg (131 mol) of N-methyl-2-pyrrolidone (NMP). , 1.07 kg (6.51 mol) of 50% sodium acetate aqueous solution was charged, and gradually heated to 235 ° C. over about 3 hours while passing nitrogen under normal pressure, 8.35 kg of water and 0.17 kg (1.7 mol) of NMP. ) Was distilled off, and then the reaction vessel was cooled to 160 ° C. During this operation, hydrogen sulfide was scattered outside the 1.6 mol system.

Next, 11.9 kg (81.0 mol) of p-dichlorobenzene (p-DCB) and 10.5 kg (106 mol) of NMP were additionally added, and the reaction vessel was sealed under nitrogen gas. The temperature was raised from 200 ° C. to 270 ° C. at a rate of 0.6 ° C./min with stirring at 240 rpm, and the reaction was continued at 270 ° C. for 140 minutes. Then, while cooling to 240 ° C. over 20 minutes, 2.82 kg (157 mol) of water was injected into the system, and then cooled from 240 ° C. to 210 ° C. at a rate of 0.4 ° C./min. After that, it was rapidly cooled to near room temperature.

The contents were taken out, diluted with about 33 liters of NMP, stirred at 85 ° C. for 30 minutes, and the solids were filtered off by sieving (80 mesh). The obtained solid content was similarly diluted with about 40 liters of NMP, stirred and filtered. Then, the operation of diluting with 70 liters of warm water, stirring at 70 ° C. for 30 minutes, filtering with an 80 mesh wire mesh, and collecting the solid content was repeated twice in total. The obtained solid content and 28 g of acetic acid were diluted with 70 liters of warm water, stirred at 70 ° C. for 30 minutes, and then filtered through an 80 mesh wire mesh to recover the solid content. Further, the solid content was diluted with 70 liters of warm water, stirred at 70 ° C. for 30 minutes, and then filtered through an 80 mesh wire mesh to recover the solid content. The solid content thus obtained was dried at 120 ° C. under a nitrogen stream to obtain a dried PPS. The melt flow rate of the obtained PPS was about 600 g / 10 minutes, and the inorganic chlorine content was 300 ppm.

(Example 1)
(A) Using (a-1) as a sizing agent composed of a polyfunctional compound containing a halogen in the polymer chain, a sizing agent mother liquor dissolved and dispersed in water so as to be 2% by mass was prepared and immersed. The reinforcing fiber bundle (b-1) was surface-treated with a sizing agent and dried at 230 ° C.

A matrix resin (B-1) was used as the matrix resin to be impregnated in the reinforcing fiber bundle to which the sizing agent was applied.

(I) The unidirectional fiber reinforced resin tape was manufactured by using the unidirectional fiber reinforced resin tape manufacturing apparatus 200 shown in FIG. In FIG. 2, 16 bobbins 202 wound with reinforcing fiber bundles 201 surface-treated with a sizing agent were prepared, and the reinforcing fiber bundles 201 were continuously sent out from the bobbins 202 through the thread guide 203. The continuously delivered reinforcing fiber bundle 201 was impregnated with the matrix resin 206 quantitatively supplied from the feeder 205 filled with the matrix resin in the impregnation die 204. The reinforcing fiber bundle 201 impregnated with the matrix resin 206 in the impregnated die 204 was continuously drawn from the nozzle of the impregnated die 204 at a pulling speed of 0.5 m / min. The reinforcing fiber bundle 201 pulled out by the take-up roll 207b passed through the cooling roll 207a and the matrix resin was cooled and solidified, and was taken up by the take-up machine 209 as (I) unidirectional fiber-reinforced resin tape 208. .. The obtained (I) unidirectional fiber reinforced resin tape 208 had a thickness of 0.3 mm and a width of 50 mm. The reinforcing fiber mass content of this (I) unidirectional fiber reinforced resin tape was 60.2 mass%.

After 16 layers of the obtained (I) unidirectional fiber reinforced resin tape were laminated to prepare a laminate precursor, the obtained laminate precursor was hot-pressed to obtain a laminate. At this time, 16 layers were laminated in a pseudo isotropic manner so that the laminated structure of the laminated body was [-45/0 / + 45/90] _-2S .

The laminate is placed in the center of the concave portion of the die so that the thin-walled portion is aligned with the peripheral wall surface of the concave portion, and the other convex portion of the mold is pressed by a heating die press molding machine at 260 ° C. for 90 seconds. After preheating, hot pressing was performed at 240 ° C. for 180 seconds while applying a pressure of 2 MPa. As a result, a laminated board of (I) unidirectional fiber reinforced resin tape was obtained.

This laminated board and a laminated board manufactured in the same manner as the laminated board of the (I) unidirectional fiber reinforced resin tape as a mating material of the laminated body using the (II) thermoplastic resin composition are subjected to vibration welding. The tensile strength of the integrated structure obtained by joining was measured by a lap shear test (shear test) in accordance with JIS K6851 (1994). The obtained tensile strength was used as an index of the welding strength of the integrated structure.

The obtained integrated structure had high welding strength and was at a level where there was no problem in use. Table 1 shows the configuration of the integrated structure and the evaluation results.

(Example 2)
(A) As a result of using (a-2) as a sizing agent composed of a polyfunctional compound containing a halogen in the polymer chain and (b) surface-treating the reinforcing fibers with the sizing agent in the same manner as in Example 1, the sizing agent. The blending amount of the sizing agent in the reinforcing fiber bundle surface-treated with was 0.6% by mass. Using the reinforcing fiber bundle surface-treated with this sizing agent, an integrated structure was obtained in the same manner as in Example 1. The reinforcing fiber mass content of this (I) unidirectional fiber reinforced resin tape was 60.6 mass%. The obtained integrated structure had high welding strength and was at a level where there was no problem in use. Table 1 shows the configuration of the integrated structure and the evaluation results.

(Example 3)
(A) As a polyfunctional compound containing a halogen in the polymer chain, (a-3) was used, and (b) the reinforcing fibers were surface-treated with a sizing agent in the same manner as in Example 1, and as a result, the surface was treated with a sizing agent. the amount of the sizing agent in the reinforcing fiber bundle in the became 0.7 mass%. Using the reinforcing fiber bundle surface-treated with this sizing agent, an integrated structure was obtained in the same manner as in Example 1. The reinforcing fiber mass content of this (I) unidirectional fiber reinforced resin tape was 61.5 mass%. The obtained integrated structure had high welding strength and was at a level where there was no problem in use. Table 1 shows the configuration of the integrated structure and the evaluation results.

(Example 4)
(A) (a-2) was used as the polyfunctional compound containing halogen in the polymer chain, and (B-2) was used as the polyphenylene sulfide resin as the outermost layer of the laminated board (I) unidirectional. The same as in Example 1 except that the fiber reinforced resin tape was arranged and the (I) unidirectional fiber reinforced resin tape using (B-1) as the polyphenylene sulfide resin was arranged in the other layers. A laminated board was obtained. Further, as in Example 1, as the mating material of the laminate using the (II) thermoplastic resin composition, the (I) laminated plate of the unidirectional fiber reinforced resin tape obtained in this example was used. , Obtained an integrated structure. The reinforcing fiber mass content of this (I) unidirectional fiber reinforced resin tape was 60.6%. The obtained integrated structure had high welding strength and was at a level where there was no problem in use. Table 1 shows the configuration of the integrated structure and the evaluation results.

(Example 5)
(A) A laminated board of (I) unidirectional fiber reinforced resin tape was obtained in the same manner as in Example 1 except that (a-2) was used as the polyfunctional compound containing halogen in the polymer chain. .. On the other hand, a polyphenylene sulfide resin composition (B-1) containing no reinforcing fibers was used as a mating material for the laminate using the (II) thermoplastic resin composition to obtain an integrated structure. The reinforcing fiber mass content of this (I) unidirectional fiber reinforced resin tape was 60.5%. The obtained integrated structure had high welding strength and was at a level where there was no problem in use. Table 1 shows the configuration of the integrated structure and the evaluation results.

(Comparative Example 1)
(A) Using (a-2) as a polyfunctional compound containing a halogen in the polymer chain, a sizing agent mother liquor dissolved and dispersed in water so as to be 0.5% by mass was prepared, and the same as in Example 1. Similarly (b) a result of the surface treatment with reinforcing fibers the sizing agent, the amount of the sizing agent in the reinforcing fiber bundle which has been surface treated with a sizing agent was 0.1 mass%. Using the reinforcing fiber bundle surface-treated with this sizing agent, an integrated structure was obtained in the same manner as in Example 1. The reinforcing fiber mass content of this (I) unidirectional fiber reinforced resin tape was 61.0% by mass. The obtained integrated structure had low welding strength and was at a level unsuitable for practical use. Table 2 shows the configuration of the integrated structure and the evaluation results.

(Comparative Example 2)
(A) Using (a-2) as a polyfunctional compound containing a halogen in the polymer chain, a sizing agent mother liquor dissolved and dispersed in water so as to be 4% by mass was prepared, and (b) was obtained by an immersion method. reinforcing fibers result of the surface treatment with a sizing agent, the amount of the sizing agent in the reinforcing fiber bundle which has been surface treated with a sizing agent was 2.5 mass%. Using the reinforcing fiber bundle surface-treated with this sizing agent, an integrated structure was obtained in the same manner as in Example 1. The reinforcing fiber mass content of this (I) unidirectional fiber reinforced resin tape was 60.8%. The obtained integrated structure had low welding strength and was at a level unsuitable for practical use. Table 2 shows the configuration of the integrated structure and the evaluation results.

(Comparative Example 3)
(A) As a polyfunctional compound containing a halogen in the polymer chain, (a-2) was used to (b) a sizing agent was added to the reinforcing fiber, and (B) as a polyphenylene sulfide resin, (B-3). ) Was used, and an integrated structure was obtained in the same manner as in Example 1. The reinforcing fiber mass content of this (I) unidirectional fiber reinforced resin tape was 61.2 mass%. The obtained integrated structure had low welding strength and was at a level unsuitable for practical use. Table 2 shows the configuration of the integrated structure and the evaluation results.

(Comparative Example 4)
(A) As a polyfunctional compound containing a halogen in the polymer chain, (a-2) was used to (b) a sizing agent was added to the reinforcing fiber, and (B) as a polyphenylene sulfide resin, (B-4). ) Was used, and an integrated structure was obtained in the same manner as in Example 1. The reinforcing fiber mass content of this (I) unidirectional fiber reinforced resin tape was 59.9 mass%. The obtained integrated structure had low welding strength and was at a level unsuitable for practical use. Table 2 shows the configuration of the integrated structure and the evaluation results.

(Comparative Example 5)
The integrated structure was formed in the same manner as in Example 1 except that (a) the reinforcing fibers were surface-treated with a sizing agent using (a-4) as a polyfunctional compound containing a halogen in the polymer chain. Obtained. The reinforcing fiber mass content of this (I) unidirectional fiber reinforced resin tape was 59.2 mass%. The obtained integrated structure had low welding strength and was at a level unsuitable for practical use. Table 2 shows the configuration of the integrated structure and the evaluation results.

(Comparative Example 6)
The integrated structure was formed in the same manner as in Example 1 except that (a) the reinforcing fibers were surface-treated with a sizing agent using (a-5) as a polyfunctional compound containing a halogen in the polymer chain. Obtained. The reinforcing fiber mass content of this (I) unidirectional fiber reinforced resin tape was 58.5% by mass. The obtained integrated structure had low welding strength and was at a level unsuitable for practical use. Table 2 shows the configuration of the integrated structure and the evaluation results.

11 Laminated plate of unidirectional fiber reinforced resin tape 12 Mating material of the laminate using the thermoplastic resin composition 13 Joints 14, 15 Chuck part 200 Manufacturing equipment for unidirectional fiber reinforced resin tape 201 Reinforced fiber bundle 202 Bobin 203 Thread Guide 204 Impregnated Die 205 Feeder 206 Matrix Resin 207a Cooling Roll 207b Pickup Roll 208 Unidirectional Fiber Reinforced Resin Tape 209 Winder

Claims (7)

(I) Integration formed by welding a laminated board in which a unidirectional fiber reinforced resin tape in which reinforcing fibers are aligned in one direction is laminated and (II) a mating material of the laminated board using a thermoplastic resin composition. It's a structure
The (I) unidirectional fiber reinforced resin tape unidirectionally aligns the reinforced fibers surface-treated with a sizing agent composed of a polyfunctional compound containing chlorine in the polymer chain, and impregnates the polyphenylene sulfide resin as a matrix resin. One-way fiber reinforced resin tape
The amount of the sizing agent adhered to the reinforcing fibers surface-treated with the sizing agent composed of a polyfunctional compound containing chlorine in the polymer chain is 0.2 to 2% by mass.
An integrated structure characterized in that the chlorine content in the sizing agent is 3 to 15% by mass, and the polyphenylene sulfide resin contains 30 to 250 ppm of inorganic chlorine. The integrated structure according to claim 1, wherein the reinforcing fibers surface-treated with the sizing agent occupy 20 to 70% by mass of the (I) unidirectional fiber reinforced resin tape. The integrated structure according to claim 1 or 2, wherein the sizing agent is made of an aliphatic epoxy resin. Any of claims 1 to 3, wherein the matrix resin impregnated in the unidirectional fiber reinforced resin tape arranged at least on the outermost surface layer of the laminated board has a molecular weight of 50,000 or more and less than 100,000. The integrated structure described in. The integrated structure according to any one of claims 1 to 4, wherein the thermoplastic resin composition (II) is a polyphenylene sulfide resin composition. Reinforcing fibers surface-treated with a sizing agent consisting of a polyfunctional compound containing chlorine in the polymer chain are aligned in one direction.
A unidirectional fiber reinforced resin tape impregnated with polyphenylene sulfide resin as a matrix resin.
The amount of the sizing agent adhered to the reinforcing fibers surface-treated with the sizing agent composed of a polyfunctional compound containing chlorine in the polymer chain is 0.2 to 2% by mass.
The chlorine content in the sizing agent is 3 to 15% by mass, and the chlorine content is 3 to 15% by mass.
A unidirectional fiber reinforced resin tape characterized in that the polyphenylene sulfide resin contains 30 to 250 ppm of inorganic chlorine. The unidirectional fiber reinforced resin tape according to claim 6 , wherein the sizing agent is made of an aliphatic epoxy resin.