JPH04175374A - Fiber-reinforced thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To improve the interfacial adhesion between a thermoplastic resin and a fibrous material and remarkably improve the heat resistance, impact strength, bending strength, etc., of the resin by treating the surface of the fibrous material with a phenoxy resin before compounding the fibrous material into the resin. CONSTITUTION:The surface of a fibrous material (e. g. glass fiber) for reinforcing a thermoplastic resin is treated with a phenoxy resin soln., e.g. by dipping, spraying, or coating. The treated material is compounded into a thermoplastic resin, pref. a thermoplastic polyester (e.g. polybutylene terephthalate), a polyarylene sulfide, or a polycarbonate, to give the title compsn., which is suitably used for electric and electronic parts, automotive parts, timepiece parts, airplane materials, etc.

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention improves the adhesion of the interface between the reinforcing fiber material and the thermoplastic resin, and improves heat resistance, dimensional stability, impact resistance, strength, etc. This relates to fiber-reinforced thermoplastic resin compositions that have excellent mechanical properties, and are used in injection molded products, compression molded products, extrusion molded products, etc., and are used in various electrical and electronic parts, mechanical parts, automobile parts, sports equipment, miscellaneous goods, etc. It is used for the following purposes.

<Conventional technology> Fiber-reinforced plastics (FRP) have excellent mechanical properties such as heat resistance, dimensional stability, elastic modulus, and strength, so they are used for electrical and electronic parts, leisure goods, automobiles, and aircraft. It is used in a wide range of fields including parts and construction materials, and is attracting attention as a material that can replace metals. However, most of the plastics used in FRP are thermosetting resins, and despite the fact that thermoplastic resins have a greater variety and are produced in far greater quantities than thermosetting resins, they are rarely produced. Currently, it is not used as FRP.

<Problems to be solved by the invention> In the case of FRP, the adhesion of the interface between the fiber material and the resin is an important point for exhibiting excellent performance. In thermosetting resins, a trifunctional coupling agent that reacts with both the resin and the fiber material is used as a surface treatment agent to improve the adhesion between the two, but in the case of thermoplastic resins, the adhesion between the two is improved. Because there is almost no chemical activity on the side, it is not possible to form chemical bonds with reactive coupling agents like thermosetting resins and improve the adhesion of the interface. This is the biggest reason why this is not the case. Many attempts have been made to improve the adhesion of the interface between thermoplastic resins and fiber materials, but most of them are based on silanes that are expected to be reactive with resins like those used in thermosetting resins. Currently, sufficient effects are not obtained because coupling agents such as chromium-based, chromium-based, titanate-based, etc. are used. Also,
There is also a method of using adhesive resin such as polyurethane as a treatment agent, but polyurethane has a thermal decomposition temperature of 200°C.
Because of the relatively low degree of thermal decomposition, the influence of thermal decomposition becomes a problem when molding materials such as polyarylene sulfide and polyamide at temperatures above 200°C.

The purpose of the present invention is to improve the adhesion between a thermoplastic resin and a fiber material, thereby creating a heat-resistant material with excellent heat resistance, chemical resistance, and dimensional stability, as well as improved mechanical properties such as impact resistance and strength. The present invention provides a plastic resin composition.

Means for Solving the Problems> That is, the present invention provides thermoplastic resins, particularly polyarylene sulfides, thermoplastic polyesters, polyarylene sulfides, and polyarylene sulfides.
By using a fiber material whose surface is treated with phenoxy resin for at least one thermoplastic resin selected from resin, polycarbonate, polyamide, ABS resin, polyacetal, polysulfone, polyphenylene oxide, polyether ketone, and polyetherimide. The present invention relates to the fiber-reinforced thermoplastic resin composition obtained.

The phenoxy resin used in the present invention has excellent compatibility and affinity with many thermoplastic resins including the above-mentioned thermoplastic resins, and also has high affinity with various fibers such as glass fiber. It is expected that by treating the fiber surface with this resin, the adhesion between the thermoplastic resin and the fiber material will be improved, and as a result, the mechanical properties will be improved. In addition, phenoxy resin has a thermal decomposition temperature of 400
°C or higher, and has excellent thermal stability.

As the thermoplastic resin used in the present invention, any of the various thermoplastic resins described in known literature can be used, but from the viewpoint of compatibility and affinity with phenoxy resin, polyarylene sulfide, thermoplastic polyester , polycarbonate, boriasorate, polyamide, ABS
Preferred are resins such as polyacetal, polysulfone, polyphenylene oxide, polyetherketone, and polyetherimide.

The polyarylene sulfide (PAS) used in the present invention is a polymer represented by the structural formula (-A r-3-) n [A r :arylene group], and especially the arylene group (
-Ar-) is p-phenylene.

It is at least one kind of polymer shown in These include, for example, Japanese Patent Publication No. 45-3368 and U.S. Patent No. 381
No. 9582, US Pat. No. 4], US Pat. No. 02,875.

The polymer may be a substantially linear polymer, a partially crosslinked polymer, or a mixture thereof.

In addition, PAS is a homopolymer having the above structure,
As part of the arylene group (-Ar-), m-phenylene,
It can also contain 0-phenylene, 2,6-naphthalene, 4,4-biphenylene, etc., or a copolymer. Furthermore, copolymers (random copolymers, block copolymers, and graft copolymers) of polyphenylene sulfide and polyphenylene sulfide ketone, or polyphenylene sulfide and polyphenylene sulfide sulfone (random copolymers, block copolymers, and graft copolymers) are also included.

The heating agent V polyester includes terephthalic acid, inphthalic acid, orthophthalic acid, natutaledicarphonic acid, 4.4-
-Diphenylenecarboxylic acid, diphenylether dicarboxylic acid, α,β-bis(4-carboxyphenoxy)ethane, adipic acid, cehatic acid, azelaic acid, decanedicarboxylic acid, ゛dodecanedicarboxylic acid, cyclohexylcarboxylic acid acids, dicarboxylic acids such as dimer acids, or their ester-forming derivatives, ethylene glycol, propylene glycol, phthanol, bentanediol, neopentyl glycol, hexanediol, octanediol, tecanshiol, cyclohexane dimetatool, hytruquinone, bisphenol A, 2.
Polyester obtained from glycols such as 2-bis(4-hydro-7ethoxyphenyl)furopane, golden gelatin, polyethylene ether glycol, polytetramethylene ether glycol, and aliphatic polyester oligomers having hydroxyl groups at both ends. Usually, the intrinsic viscosity (η) measured at 30°C in a mixed solvent of phenol and tetrachloroethane in a weight ratio of 6:4 is 0.1
A range of 3 to 1.5 dQ/g is used.

In addition, as comonomer components, hydroxycarboxylic acids such as glycolic acid, hydroxybutyric acid, hydroxybenzoic acid, hydroxyphenylacetic acid, and naphthylglycolic acid, lactone compounds such as propiolactone, butyrolactone, valerolactone, and caprolactone, or thermoplastic To the extent possible, polyfunctional ester-forming components such as trimethylolpropane, trimethylolethane, glycerin, pentaerythritol, trimellitic acid, trimesic acid, and pyromellitic acid may be included.

Also, dibromoterephthalic acid, tetrabromoterephthalic acid, tetrabromophthalic acid, tetrachloroterephthalic acid, 1. Aromatic compounds such as 4-dimethyloltetrabromobenzene, tetrabromobisphenol A1, and ethylene oxide adducts of tetrabromobisphenol A have a chlorine compound such as chlorine or bromine as a substituent, and an ester-forming group. Also included is a thermoplastic polyester copolymerized with a halogen compound.

Particularly preferable heating material V-type polyesters include polyethylene terephthalate, polybutylene terephthalate,
Polyhexamethylene terephthalate, poly(ethylene/
butylene terephthalate), poly(cyclohexane dimethylene terephthalate), poly(butylene/tetramethylene terephthalate), 2,2-bis(β-hydroxytetrabromophenyl)propane copolymerized polybutylene terephthalate, and the like.

Polycarbonate (PC) can be homogeneous PC or PC based for example on one or more of the following bisphenols:
C copolymer can be used. hydroquinone, resorcinol,
Dihydroxydiphenyl, bis-(hydroxyphenyl)-alkane, bis=(hydroxyphenyl)-cycloalkane, bis-(hydroxyphenyl)-sulfide, bis-(hydroxyphenyl)-ketone, bis-(
hydroxyphenyl)-ether, bis-(hydroquinphenyl)-sulfoxide, bis-(hydroxyphenyl)-sulfone and α.

α-bis-(hydroxyphenyl)-diisopropylbenzene and compounds thereof substituted with alkyl or halogen in the nucleus.

Among these, specific examples of preferable bisphenols include 4,4-dihydroxydiphenyl, 2,2-bis-(4-hydroxyphenyl)-furopane, and 2.4-Q
su(4-hydroxyphenyl)-2-methylbutane,
1,1-bis-(4-hydroxyphenyl)-cyclohexane, α,α-bis-(4-hydroxyphenyl)
-p-diisopropylbenzene, 2,2-bis-(3-
Methyl-4-hydroxyphenyl)-propane, 2,2
-bis-(3-chloro-4-hydroxyphenyl)-propane, bis=(3,5-dimethyl-4-hydroxyphenyl)-methane, 2,2-bis-(3,5-dimethyl-4-hydroxyphenyl) )-propane, 2,2-bis-(3,5-dimethyl-4-hydroxyphenyl)-sulfone, 2,4-bis-(3,5-dimethyl-4-hydroquinphenyl)-2-mercaptan, 1 ．． 1-His-(3,5-dimethyl-4-hydroxyphenyl)-
Cyclohexane, α,α-bis-(3,5-dimethyl-4-hydroxyphenyl)-p-diisopropylbenzene, 2,2-bis-(3,5-dichloro-4-hydroxyphenyl)-propane and 2, 2-bis-(3,
5-dibromo-4-hydroxyphenyl)-propane, etc., preferably 2,2-bis-(4-hydroxyphenyl)propane, 2,2-bis-(3,5-dimethyl-4-hydroxyphenyl) )-propane, 2.2
-bis-(3,5-dichloro-4-hydroxyphenyl)-propane, 2,2-bis=(3゜5-dibromo-4
-hydroxyphenyl)propane and 1,1-bis-
(4-Hydroquinphenyl)-cyclohegyosan is mentioned.

Preferred PCs are those based on the preferred bisphenols described above. A particularly preferred PC copolymer is 2,2-bis-
A copolymer of (4-hydroxyphenyl)-propane and one of the other particularly preferred bisphenols mentioned above.

Other particularly suitable PCs are 2,2-bis-(4-hydroxyphenyl)-propane or 2,2-bis-(3,5-
It is based solely on dimethyl-4-hydroxyphenyl)-propane.

Note that PC can be produced by a known method, such as melt transesterification and reaction of bisphenol and diphenyl carbonate, and two-phase interfacial polymerization of bisphenol and phosgene.

Polyarylates are synthesized from bisphenols or derivatives thereof and dibasic acids or derivatives thereof. Examples of bisphenols include 2,2-bis-(4-hydroxyphenyl)-propane, 4,4-dihydroxy-diphenyl ether, 4,4-dihydroxy-3,3-
-dimethyldiphenyl ether, 4.4=-dihydroxy-3,3-dichlorodiphenyl ether, 4.4--
Dihydroxy-diphenyl sulfide, 4,4-monodihydroxy-diphenyl sulfone, 4,4-dihydroxy-diphenyl ketone, bis-(4-hydroxyphenyl)-methane, 1,1-bis=(4-hydroxyphenyl)-ethane , 1.1-bis-(4-hydroxyphenyl)-n-butane, di(4-hydroxyphenyl)-
Cyclohexyl-methane, 1,1-bis-(4-hydroxyphenyl)-2,2,2-1-IJchloroethane, 2,2-bis-(4-hydroxy-3,5-dibromophenyl)-propane, 2 .2-bis-(4-hydroxy-3,5-dichlorophenyl)-propane, etc., but particularly preferred is 2,2-bis-(4-hydroxyphenyl)-propane, that is, bisphenol A. be.

Examples of dibasic acids include aromatic radicals, bonic acids such as isophthalic acid, terephthalic acid, bis-(4-carboxy)-diphenyl, bis-(4-carboxyphenyl)
-ether, bis-(4-carboxyphenyl)-sulfone, bis-(4-carboxyphenyl)-carbonyl, bis-(4-carboxyphenyl)-methane, bis=
(4-carboxyphenyl)-dichloromethane, 1,2
- and 1,1-bis-(4-carboxyphenyl)-
Ethane, 1,2- and 2,2-bis=(4-carboxyphenyl)-propane, 1,2- and 2,2-bis-(4-carboxyphenyl)-1,1-dimethylpropane, 1,1 - and 2,2-bis=(4-carboxyphenyl)-butane, 1,1- and 2,2-bis-(
4-carboxyphenyl)-pentane, 3,3-bis-
(4-carboxyphenyl)-hebutane, 2,2-bis-(4-carboxyphenyl)-hebutane; and aliphatic acids such as oxalic acid, adipic acid, succinic acid, malonic acid,
Examples include cepatic acid, geltaric acid, azelaic acid, and speric acid, but isophthalic acid and terephthalic acid or mixtures of these derivatives are preferred.

Examples of the polyamide include various well-known polyamides. For example, oxalic acid, adipic acid, speric acid, sebacic acid,
Terephthalic acid, isophthalic acid Ll.

Polycondensation of a dicarboxylic acid such as 4-cyclohexyldicarboxylic acid and a diamine such as ethylenediamine, pentamethylenediamine, mexamethylenediamine, decamethylenediamine, 1,4-cyclohexyldiamine, m-xylenediamine Examples include polyamides obtained by polymerizing cyclic lactams such as caprolactam and laurinlactam; and polyamides obtained by copolymerizing cyclic lactams, dicarboxylic acids, and diamine salts. Among these polyamides, preferably nylon 6, nylon 66, MXD6
Nylon (copolymer of m-xylene diamine and adipic acid), 6.1O nylon, 66/6.10 nylon,
6/66 nylon, 12 nylon, 11 nylon, 6/
Examples include 6T nylon (copolymer of salts of caprolactam, terephthalic acid, and hexamethylene diamine), and two or more types of these polyamides may be used in combination. Particularly suitable materials include 6 nylon, 66 nylon, and 46 nylon.
nylon, and MXD6 nylon.

ABS resin is a graft copolymer obtained by polymerizing two or more compounds selected from vinyl cyanide compounds, aromatic vinyl compounds, and unsaturated carboxylic acid alkyl ester compounds in the presence of a conjugated diene rubber. It is. Furthermore, if necessary, a copolymer obtained by polymerizing two or more compounds selected from vinyl cyanide compounds, aromatic vinyl compounds, and unsaturated carboxylic acid alkyl ester compounds can be contained. The conjugated diene rubber in the graft copolymer includes polybutadiene, butadiene-styrene copolymer, butadiene-acrylonitrile copolymer, etc., and the vinyl cyanide compound includes:
Examples of the aromatic vinyl compound include styrene, vinyltoluene, dimethylstyrene, chlorostyrene, and particularly preferably α-methylstyrene. Examples of unsaturated carboxylic acid alkyl ester compounds include methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, and hydroxyl acrylate.

Polyacetal (POM) has the general formula It is a polyether represented by [-RCHO-]n.

There are two types of POM: homopolymers and copolymers. A homopolymer is one in which R=H and is a polymer of formaldehyde, and a copolymer is a polymer of trioxane, which is a ring 31 of formaldehyde, copolymerized with a small amount of ethylene oxide. Commercially available products of polyacetal include homopolymer types such as Tenac manufactured by Asahi Kasei Corporation and Delrin manufactured by DuPont, and homopolymer types such as Ginilacon manufactured by Polyplastics and Ubital manufactured by Mitsubishi Gas Chemical Company.

Polyphenylene oxide (PPO) is also called polyphenylene ether (PPE) and has the following general formula [
It can be obtained by polycondensing one or more types of monocyclic phenols represented by 1.

R2RI (However, R1 is a lower alkyl group having 1 to 3 carbon atoms, R2 and R1 are hydrogen or a lower alkyl group having 1 to 3 carbon atoms, and a lower alkyl substituent is always present at the ortho position of at least one of the hydroxyl groups. ) This PPO may be a homopolymer or a copolymer.

Examples of the monocyclic phenol represented by the above general formula [1] include 2,6-dimethylphenol, 2,6-diethylphenol, 2,6-dipropylphenol, 2-
Methyl-6-ethylphenol, 2-methyl-6-propylphenol, 2-ethyl-6-propylphenol, m-cresol, 2,3-dimethylphenol, 2,
3-diethylphenol, 2,3-dipropylphenol, 2-methyl-3-ethylphenol, 2-methyl-
3-7” Lobylphenol, 2-ethyl-3-methylphenol, 2-ethyl-3-propylphenol, 2-
Propyl-3-methylphenol, 2-propyl-3-
Ethylphenol, 2,3゜6-drimethylphenol, 2. 3. 6-Driethylphenol, 2. 3.
Examples include 6-driprobylphenol, 2,6-dimethyl-3-ethylphenol, and 2,6-dimethyl-3-propylphenol.

The PPO obtained from this is, for example, poly(2,
6-dimethyl-1,4-phenylene)ether, poly(
2,6-diethyl-1,4-phenylene) ether, poly(2,6-dipropyl-1,4-)unicine) ether, poly(2-methyl-6-nityl-1,4-phenylene) ) ether, poly(2-methyl-6-broby-1,4-phenylene) ether, poly(2-ethyl-
6-broby-1,4-phenylene)ether, 2.6
-Simethylphenol/2. 3. 6-) Limethylphenol copolymer, 2,6-dimethylphenol/2.
3. 6-Driethylphenol copolymer, 2.6-
Diethylphenol/2. 3. 6-) Limethylphenol copolymer, 2.6-diprobylphenol/2.
3. 6-dimethylphenol copolymer, poly(2,6-dimethyl-1゜4-)unicine) ether, 2,6-dimethylphenol/2. 3. 6-) Copolymers obtained by graft-polymerizing styrene onto a trimethylphenol copolymer and the like can be mentioned.

In particular, preferred PPO for use in the present invention is poly(2,
6-dimethyl-1,4-)unicine)ether, 2,6
-Simethylphenol/2. It is a 3°6-dolimethylphenol copolymer.

Polysulfones are defined as polyarylene compounds in which the arylene units are located in a disordered or ordered manner, with ether and sulfone linkages, such as:
Structural formula of ~@ (in the formula, -φ- represents a p-phenylene group, -
(Ph represents a phenyl group and n represents an integer of 10 or more), but preferably those having a structure of ■ or ■. These may be a single substance or a block copolymer. As a block copolymer,
There are block copolymers of (1) and (2), block copolymers of (2) and polycarbonate, and block copolymers of (2) and arylate.

■　(−φ−0−φ−3O2−)ゎ ■ (-φ-φ-3O2-).

■ (-SO2-φ-0-φ-5O2-φ-CH2-φ
-).

■ (−φ−c(cHs)2−φ−〇−φ−8○2−φ
--0-).

Hs ■ (-〇-φ-C-φ-〇-φ-802-φ-)9P
h ■ (−〇−φ−CH2−φ−O−φ−5O2−φ−)
A■ (-o-φ-0-φ-8○2-φ-).

@) (−〇−φ−CO−φ−0−φ−5o2−φ−
)Sh ■ (−〇−φ−C−φ−○−φ−3 O2−φ−).

h ■ (-〇-φ-0-φ-0-φ-S O2-φ-).

0 (−〇−φ−so, −φ−〇−φ−CF, −φ−)
, @(-0-3O2-φ-φ-3 O,-φ-0-J5
-0--φ-C(CHs)2-φ-0-).

■ (−φ−3O2−φ−〇−φ−8o2−φ−0−φ
−−c (CHI) 2−φ−○−)ゎ＠ (−φ
−SO, −φ−〇−φ−3O2−φ−), 1■ (−φ
-φ-〇-φ-3 O2-φ-0-).

[Phase] (-φ-○-φ-8O3-φ-φzu02-) The polyetherketone is composed of a repeating unit of the following formula [2] and/or a repeating unit of the following formula [3] alone. or with other repeating units and has an intrinsic viscosity (1, V,
) is 0.7 or more.

Other repeating units other than the above formula [2 and/or formula [3] include formula [4] [where A is a direct bond, oxygen, sulfur, -SO, -1-c]
It is an o- or divalent hydrocarbon group. ] and formula [5] [5] Furthermore, as a copolymer unit, formula [
6 and formula [7] in the ortho or rose position relative to the group Y or Y-,
Y and Y- are the same or different, -〇〇- or -8
02-, Ar- is a divalent aromatic group, and n is 0, 1.2 or 3. ) is included.

Polyetherimide has the following formula.

[8 In the above formula, -0-Ql-〇- is 3 or 4 and 3-
or bonded to the 4- position, Ql is puK"-"
-""°1 or (Q"), -"ΣXQ3be(Q-)□-" [11] Selected from divalent substituted or unsubstituted aromatic derivative groups. Here, Q- is independently C3-C, alkyl, aryl or halogen. Q, is -〇-1-S-1
-co-, -so, -1-8O-1 cycloalkylene having 1 to 6 carbon atoms 1. Q is selected from alkylidene having 1 to 6 carbon atoms or cycloalkylidene having 4 to 8 carbon atoms;
Aromatic hydrocarbon radicals having 6 to 20 carbon atoms and their halogenated derivatives (wherein the alkyl group contains 1 to 6 carbon atoms), alkylene and cycloalkylene having 2 to 20 carbon atoms It is a polydiorganosiloxane having C3-C, alkylene as a terminal group or the above formula [11].

In the present invention, among the above-mentioned preferred thermoplastic resins, polyarylene sulfide and thermoplastic polyester resins can be particularly preferably applied. Furthermore, any blend of resins can be applied, and among them,
It is preferably applied to compositions containing polyarylene sulfide or compositions containing thermoplastic polyester.

In addition, since polyacetal has difficulty in thermal stability, 25
Blending with resins such as polyarylene sulfide, thermoplastic polyester, polycarbonate, polyarylate, polysulfone, and polyamide, which are molded at temperatures above 0°C, is virtually impossible.

On the other hand, the phenoxy resin used as a surface treatment agent for fiber materials in the present invention includes dihydric phenols, bisphenols such as bisphenol A1 bisphenol F1 tetrachlorbisphenol, diphenolic acid, and a condensate of bisphenol and p-xylene dichloride. It is a thermoplastic polyether that does not have epoxy groups at either end and is synthesized by the reaction of a diol compound with an epoxy compound such as shrimp chlorohydrin, butadiene oxide, or a glycidyl compound. Among these, those synthesized using bisphenol A and epichlorohydrin as main raw materials are preferred.

Preferred phenoxy resins for use in the present invention have a solution viscosity of 40% non-volatile content in methyl ethyl ketone (MEK) solution in the range of 5 x 102 to 10' cps, preferably 103 to 5 x 10' cps.

Commercially available products include UCAR phenoxy (grades PKHH, PKHJ) manufactured by Union Carbide.

PKHC, etc.).

Regarding the amount of phenoxy resin used for surface treatment,
It varies depending on the type of fiber used and fiber diameter, so -
Although it cannot be generally specified, the weight ratio of the fiber material is 0.1
~5% by weight, preferably 0.3-3% by weight is used. If it is less than 0.1% by weight, almost no surface treatment effect will be observed, and if it exceeds 5% by weight, the strength etc. of the composition will decrease, which is not preferable.

As for the surface treatment of the fibrous material, conventional methods such as dissolving the phenoxy resin in a solvent and impregnating it, coating or spraying it, and melting and impregnating it can be used.

The fiber materials used in the present invention are generally thermoplastic resin materials such as carbon fiber, glass fiber, silane glass fiber, silica fiber, alumina fiber, aramid fiber, boron fiber, whisker, ceramic fiber, asbestos fiber, and metal fiber. Short fibers, long fibers, or woven fibers used for fiber reinforcement are used.

The blending amount of the fiber material cannot be specified in part because it varies depending on the type of thermoplastic resin used, the type of fiber used, fiber length, fiber diameter, type of fabric, and purpose of use. Usually, 20 to 300 parts by weight is used per 100 parts by weight of the thermoplastic resin.

In the present invention, the granular reinforcing agent is not an essential component, but it can be blended as necessary, and it can be added to the thermoplastic resin 1.
Usually, 10 parts by weight or less is used per 00 parts by weight. Particulate reinforcing agents include silicates and carbonates such as mica and talc, sulfates, metal oxides, glass beads, and silica. Two or more of these may be used in combination.

In addition, as additives, small amounts of mold release agents, colorants, heat stabilizers, ultraviolet stabilizers, foaming agents, rust preventives, epoxy resins, phenolic resins,
Thermosetting resins such as polyimide can be used in combination.

The method of impregnating the surface-treated reinforcing fiber material into the thermoplastic resin is not particularly specified, but the method varies depending on the shape of the fibers used and the like. For example, in the case of short fibers such as milled or chopped fibers, the method is to melt-knead them with a thermoplastic resin using a normal extruder and pelletize them, but to create a UD mat using long fibers, the method is to melt and impregnate the thermoplastic resin. When a fiber fabric such as a swirl mat or a cross mat is used, a common method is to melt and impregnate a thermoplastic resin in the form of a film. Note that the melting temperature at which the thermoplastic resin is melted and impregnated varies depending on the resin used.

<Examples> The present invention will be specifically explained below using Examples, but the present invention is not limited only to these Examples.

Example 1 Glass fibers having a fiber diameter of approximately 12 μm and a fiber length of 3 mm were impregnated with a 1% phenoxy resin solution of methyl ethyl ketone (MEK) and surface treated. The surface-treated glass fibers were allowed to stand at room temperature for 24 hours, and then vacuum-dried at 100°C for about 2 hours. The amount of phenoxy resin adsorbed onto the glass fibers was about 1% by weight.

To 100 parts by weight of polybutylene terephthalate (PBT), 40 parts by weight of the above-treated glass fiber was added, melted and kneaded at 250°C using an extruder to form a pellet, and then injected. A sample piece was made using a molding machine. Using this, an Izot impact test (no notch) and a bending test were conducted. The results are shown in Table-1. In addition, the fractured surface of the sample piece subjected to the Izotsu impact test was examined using an electron microscope (S
When observed by EM), the adhesion between the resin and the fibers was good.

In addition, PBT is Planatsuk manufactured by Dainippon Ink Chemical Co., Ltd.
BT-120 was used, and the phenoxy resin was UCAR Phenokine Grade PKHH (ME
The solution viscosity of 40% solids in K is 4500-7000
c p' s ) was used. Izotsu test is JI
S (K7110), and the bending test was in accordance with JIS (K7055).

Comparative Example I Chopped strand CSO3MA41 manufactured by Asahi Fiberglass Co., Ltd., which is commercially available as glass fiber for PBT.
The same study as in Example 1 was conducted using Example 9. The results are shown in Table-1. Furthermore, when the fractured surface of the sample subjected to the Izot impact test was observed using an SEM, it was found that the glass fibers appeared to have come completely out of the resin.

Example 2 Polyethylene terephthalate (PE,
The same study as in Example 1 was conducted using T). The results are shown in Table-1. Furthermore, when the fractured surface of the sample piece subjected to the Izot impact test was observed using SEM, it was found that the adhesion between the resin and the fiber was good.

In addition, PET is Mitsui PET manufactured by Mitsui Pet Resin Co., Ltd.
J125 was used.

Comparative Example 2 The same study as in Example 2 was conducted using chopped strand CSO3MA419 manufactured by Asahi Fiberglass Co., Ltd. as the glass fiber. The results are shown in Table-1. In addition, the fracture surface of the sample subjected to the Izotsu impact test was analyzed using SEM.
When observed, it was as if the glass fiber had completely slipped out of the resin.

Example 3 80 parts by weight of the glass fiber used in Example 1 was added to 100 parts by weight of polyphenylene sulfide (PPS).
After melt-kneading and pelletizing at 320°C using an extruder, sample pieces were prepared using an injection molding machine, and the Izot impact test (without notches) and bending test were conducted in the same manner as in Example 1. .

The results are shown in Table-1. Furthermore, when the fractured surface of the sample piece subjected to the Izot impact test was observed using SEM, it was found that the adhesion between the resin and the fibers was good.

The PPS used had a dynamic viscosity [η'] of about 1000 poise at 300°C and 10 rad/sec.

Comparative Example 3 Chopped strand C303MA40 manufactured by Asahi Fiberglass Co., Ltd., which is commercially available as glass fiber for PPS
The same study as in Example 3 was conducted using Example 4. The results are shown in Table-1. Furthermore, when the fractured surface of the sample subjected to the Izot impact test was observed using an SEM, it was found that the glass fibers appeared to have completely come out from the resin.

Example 4 80 parts by weight of the glass fiber used in Example 1 was added to 100 parts by weight of nylon-66 to 2806C using an extruder.
After melt-kneading and forming into a pellet shape, sample pieces were prepared using an injection molding machine, and the same study as in Example 1 was conducted. The results are shown in Table-1.

Furthermore, when the fractured surface of the sample piece subjected to the Izot impact test was observed using SEM, it was found that the adhesion between the resin and the fiber was good.

Nylon-66 is YDYN manufactured by Monsanto.
E22H was used.

Comparative Example 4 Commercially available glass fiber for nylon-66,
Chiyo Sopdostrand CS manufactured by Asahi Fiberglass Co., Ltd.
The same study as in Example 4 was conducted using O3MA416. The results are shown in Table-1.

Furthermore, when the fractured surface of the sample subjected to the Izot impact test was observed using a SEM, it was found that the adhesion between the glass fiber and the resin was poor.

Example 5 100 parts by weight of modified polyphenylene oxide (modified PP0) and 60 parts by weight of the glass fiber used in Example 1 were melt-kneaded at 350'C using an extruder to form pellets, which were then injected. A sample piece was created using a molding machine, and the same study as in Example 1 was conducted. The results are shown in Table-1. Furthermore, when the fractured surface of the sample piece subjected to the Izot impact test was observed using SEM, it was found that the adhesion between the resin and the fiber was good.

The modified PPO is Iupiace manufactured by Mitsubishi Gas Chemical Co., Ltd.
AV30 was used.

Comparative Example 5 Chopped strand C303MA4 manufactured by Asahi Fiberglass Co., Ltd., which is commercially available as glass fiber for PPo.
The same study as in Example 5 was conducted using No. 97. The results are shown in Table-1. Furthermore, when the fractured surface of the sample subjected to the Izot impact test was observed using an SEM, it was found that the glass fibers were easily removed, and the adhesion between the fibers and the resin was poor.

Example 6.7/Comparative Example 6.7 2% by weight of phenoxy resin was dissolved in MEK, coated on the surface of glass fiber (swarma y) using a brush, left at room temperature for 24 hours, and then heated at 100°C. It was vacuum dried for about 2 hours. The amount of phenoxy resin adsorbed onto the glass fibers was approximately 2% by weight. PPS melt-pressed at 320°C into a film and several sheets of surface-treated glass fiber masoto were stacked in a santoisoti-like shape and heated to 300°C.
A test piece with a thickness of 2 mm was prepared by pressing at a pressure of about 5 Kg/am''.

The content of glass fiber is 80 parts by weight and 120 parts by weight based on 100 parts by weight of PPS.

Using these, an Izot impact test (2), a bending test, and a measurement of interlaminar shear strength were performed. The results are shown in Table-2.

Note that, as a comparative example, a case where no phenoxy resin was coated is shown.

It can be seen that when the surface is treated with phenoxy resin, the Izo-nod impact value, bending strength, and interlaminar shear strength are improved.

Note that the interlayer shear strength was in accordance with JIS (K7057).

In addition, PPS has a dynamic viscosity of about 2000 poise at 300°C and 10 rad/see, and phenoxy resin has a
UCAR phenoxy grade PKHH manufactured by Union Carbide was used, and the glass fiber swirl mat was manufactured by Asahi Fiberglass (450 g/m2).

Example 8/Comparative Example 8 Carbon fibers having a fiber diameter of 13 μm and a fiber length of 100 μm were impregnated with a 1% phenoxy resin solution of methyl ethyl ketone (hereinafter abbreviated as MEK) and subjected to surface treatment. The surface-treated carbon fibers were left at room temperature for 24 hours and then vacuum-dried at 100°C for about 2 hours. The amount of phenoxy resin adsorbed onto the carbon fibers was approximately 2% by weight.

A sample was prepared using 80 parts by weight of carbon fiber based on 100 parts by weight of PPS in the same manner as in Example 1, and the same measurements as in Example 1 were performed. The results are shown in Table-2. Also,
The fracture surface of the sample piece subjected to the Izotsu impact test is S
When observed by EM, the adhesion between the resin and the fibers was good.

For comparison, a similar study was conducted on a sample whose surface was not treated with phenoxy resin. The results are shown in Table-2. Further, when the fractured surface of the sample subjected to the Izot impact test was observed using a SEM, it was found that the adhesion between the fiber and the resin was poor.

The resin was the same as in Example 3, and the carbon fiber was pitch-based carbon fiber manufactured by DONACARBO5-2 (DONACARBO5-2).
41) was used.

Example 9/Comparative Example 9 To 60 parts by weight of PPS used in Example 3 and 40 parts by weight of PB7 used in Example 1, 80 parts by weight of the glass fiber used in Example 1 was added, and the extruder was turned on. using 300℃
After melt-kneading and pelletizing, sample pieces were prepared using an injection molding machine, and the same study as in Example 1 was conducted. The results are shown in Table-3. Furthermore, when the fractured surface of the sample piece subjected to the Izot impact test was observed using SEM, it was found that the adhesion between the resin and the fiber was good.

As a comparative example, a case where the glass fiber used in Comparative Example 3 was used was investigated.

The results are shown in Table-3. Also. When the fractured surface of the sample subjected to the Izot impact test was observed using a SEM, it was found that the adhesion between the fiber and the resin was poor.

Example 10/Comparative Example 10 80 parts by weight of the glass fiber used in Example 1 was added to 60 parts by weight of PPS used in Example 3 and 40 parts by weight of nylon-66 used in Example 4. , using an extruder 3
After melt-kneading and pelletizing at 00°C, sample pieces were prepared using an injection molding machine, and the same study as in Example 1 was conducted. The results are shown in Table-3. Furthermore, when the fractured surface of the sample piece subjected to the Izot impact test was observed using SEM, it was found that the adhesion between the resin and the fiber was good.

As a comparative example, a case where the glass fiber used in Comparative Example 3 was used was investigated.

The results are shown in Table-3. Also. When the fractured surface of the sample subjected to the Izo-Soto impact test was observed using an SEM, it was found that the glass fibers were missing, and the adhesion between the fibers and the resin was poor.

Example 11/Comparative Example 11 80 parts by weight of the glass fiber used in Example 1 was added to 60 parts by weight of PPS used in Example 3 and 40 parts by weight of PP○ used in Example 5, and 330° using
After melt-kneading and forming into a pellet shape, sample pieces were prepared using an injection molding machine, and the same study as in Example 1 was conducted. The results are shown in Table-3. Furthermore, when the fractured surface of the sample piece subjected to the Izot impact test was observed using SEM, it was found that the adhesion between the resin and the fiber was good.

As a comparative example, a case where the glass fiber used in Comparative Example 3 was used was investigated.

The results are shown in Table-3. Furthermore, when the fractured surface of the sample subjected to the Izot impact test was observed using a SEM, the glass fibers were completely removed, and the adhesion between the fibers and the resin was poor.

Example 12/Comparative Example 12 To 60 parts by weight of PPS and 40 parts by weight of polyarylate used in Example 3, 80 parts by weight of the glass fiber used in Example 1 was added, and the mixture was heated at 330° using an extruder. After melt-kneading and pelletizing with C, sample pieces were prepared using an injection molding machine, and the same study as in Example 1 was conducted.

The results are shown in Table 3.

Furthermore, when the fractured surface of the sample piece subjected to the Izot impact test was observed using SEM, it was found that the adhesion between the resin and the fiber was good.

As a comparative example, a case where the glass fiber used in Comparative Example 3 was used was investigated.

The results are shown in Table-3. Also. When the fractured surface of the sample subjected to the Izot impact test was observed using a SEM, it was found that the adhesion between the fiber and the resin was poor. The polyarylate is U-Polymer U-1 manufactured by Unitika Co., Ltd.
00 was used.

Example 13/Comparative Example 13 60 parts by weight of PP3 used in Example 3, polysulfone 4
80 parts by weight of the glass fiber used in Example 1
Add parts by weight, melt knead at 330°C using an extruder,
After pelletizing, sample pieces were prepared using an injection molding machine, and the same study as in Example 1 was conducted. The results are in the table-
Shown in 3.

As a comparative example, a case where the glass fiber used in Comparative Example 3 was used was investigated.

The polysulfone is UDE-LP manufactured by Amoco.
-1050 was used.

Example 14/Comparative Example 14 60 parts by weight of PPS used in Example 3, ABS resin 4
80 parts by weight of the glass fiber used in Example 1 was added to 0 parts by weight ffi, melted and kneaded at 330°C using an extruder to form pellets, and then molded into sample pieces using an injection molding machine. was prepared, and the same study as in Example 1 was conducted. The results are shown in Table-3.

As a comparative example, a case where the glass fiber used in Comparative Example 3 was used was investigated.

The ABS resin is MUSM-3 manufactured by Kanebuchi Chemical Industry Co., Ltd.
000 was used.

<Effects of the invention> The fiber-reinforced thermoplastic resin composition obtained by the present invention has the following properties:
The adhesion between the resin and fiber interface has been significantly improved.
Excellent heat resistance, chemical resistance, dimensional stability, etc., impact resistance,
Mechanical properties such as interlaminar shear strength and bending strength are significantly improved compared to conventional products. Therefore, the composition of the present invention can be used, for example, in electrical and electronic parts such as connectors and printed circuit boards, automotive parts such as lamp reflectors and various electrical components, materials for various buildings, automobiles, and aircraft, tennis rackets, etc.
Injection molding, extrusion molding, and compression molding of leisure and sports equipment such as skis, golf clubs, and fishing rods, precision parts such as OA equipment parts, camera parts, and watch parts, as well as composite sheets, stampable sheets, pipes, and sheets. It can be used as a suitable molding material in various molding fields such as pultrusion and pultrusion.

Claims (1)

[Scope of Claims] 1. A fiber-reinforced thermoplastic resin composition comprising a thermoplastic resin and a fibrous material surface-treated with phenoxy resin. 2. The fiber-reinforced thermoplastic resin composition according to claim 1, wherein a thermoplastic polyester is used as the thermoplastic resin. 3. The fiber-reinforced thermoplastic resin composition according to claim 1, wherein polyarylene sulfide is used as the thermoplastic resin. 4. The fiber-reinforced thermoplastic resin according to claim 1, wherein the thermoplastic resin is at least one selected from polyarylate, polycarbonate, polyamide, ABS resin, polyacetal, polysulfone, polyphenylene oxide, polyetherketone, and polyetherimide. Composition. 5. As the thermoplastic resin, at least one selected from (A) thermoplastic polyester and (B) polyarylene sulfide, polyarylate, polycarbonate, polyamide, ABS resin, polysulfone, polyphenylene oxide, polyether ketone, and polyetherimide. The fiber-reinforced thermoplastic resin composition according to claim 1, comprising: 6. A composition of (A) polyarylene sulfide and (B) at least one selected from polyarylate, polycarbonate, polyamide, ABS resin, polysulfone, polyphenylene oxide, polyether ketone, and polyetherimide as a thermoplastic resin. The fiber-reinforced thermoplastic resin composition according to claim 1, comprising: