JP2012149120A - Emulsion, binder for glass fiber, glass fiber, and glass fiber reinforcement polyolefin resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an emulsion and a binder for glass fiber which excel in adhesion and a binding property with the glass fiber, can improve the adhesive of the glass fiber and a polyolefin resin, and can improve the mechanical strength of a glass fiber reinforcement polyolefin resin, and to provide a glass fiber the surface of which is imparted with the same.SOLUTION: The emulsion includes a silane modification polyolefin resin in a liquid as a solid content, wherein the silane-modified polyolefin resin is a polyolefin resin in which 0.5-10 wt.% of an unsaturated silane compound is grafted, the weight average molecular weight (Mw) of the silane modification polyolefin resin is at least 50,000 and at most 300,000, and the flexural modulus based on JIS K7171 (1994) is at least 1,200 MPa and at most 3,000 MPa.

Description

  The present invention relates to an emulsion and a glass fiber sizing agent used as a glass fiber sizing agent particularly suitable as a polyolefin resin reinforcing material, a glass fiber provided with the same, and a glass fiber reinforced polyolefin resin using the glass fiber. Relates to the composition.

  In general, glass fibers are formed by drawing molten glass from a number of nozzles provided at the bottom of a platinum bushing. After a sizing agent is applied to the surface of each glass fiber (glass filament), several hundred to several thousand are used. This is bundled into one strand. Further, the glass fiber reinforced thermoplastic resin composition can be obtained by cutting the strand obtained as described above into a predetermined length, or winding the strand once and then drawing out and cutting it into a predetermined length. It is manufactured by making a chopped strand and then kneading it with a thermoplastic resin while heating.

Conventionally, many modified polyolefin resin emulsions have been used as glass fiber sizing agents used as reinforcing agents for polyolefin resins such as polyethylene and polypropylene (for example, Patent Documents 1 to 5).
Here, in Patent Document 1, a sizing agent containing an aqueous emulsion of a low molecular weight unsaturated dicarboxylic acid-modified polypropylene resin is used, and the adhesive strength between the glass fiber and the polyolefin resin is excellent. The inferior focusing power remains a problem.
In Patent Document 2, a sizing agent comprising two types of acid-modified polyolefin resins having different molecular weights and a silane coupling agent is used. In Patent Document 3, an unsaturated carboxylic acid-modified polyolefin resin and an aminosilane coupling agent are used. In Patent Document 4, a sizing agent comprising an acid-modified olefin resin neutralized with an amine and a silane coupling agent having an amino group is used.

  All of the techniques of these Patent Documents 2 to 4 are basically a combination of a polyolefin modified with an acid or an acid anhydride and a silane coupling agent. The focusing force was not sufficient, and further, the mechanical strength of the glass fiber reinforced resin was not sufficient. This is probably because the acid-modified polyolefin resin as the sizing agent was not functioning effectively because the bond between the glass fiber and the polyolefin as the matrix was formed through the silane coupling agent.

Further, Patent Document 5 describes a glass fiber reinforced composite obtained by impregnating a modified polypropylene itself with a glass mat. The purpose of the composite is to improve the confidentiality when stamping the composite. However, it was not intended to improve the converging property of the glass fiber or the mechanical strength of the glass fiber reinforced resin.
As described above, conventionally, it is excellent in adhesiveness and converging property with glass fiber, can improve the adhesiveness between glass fiber and polyolefin resin, and seems to be able to improve the mechanical strength of glass fiber reinforced resin. No glass fiber sizing agent has been found.

JP-A-6-107742 JP 2005-170691 A JP-A-7-309979 JP 2003-253563 A JP-A-62-57428

  The present invention has been made in view of the above situation, and its purpose is excellent in adhesiveness and converging property with glass fiber, and can improve the adhesiveness between glass fiber and polyolefin resin. An object of the present invention is to provide an emulsion and a glass fiber sizing agent capable of improving the mechanical strength of a polyolefin resin, and a glass fiber provided with the same.

  As a result of earnestly examining the solution of the above problems, the present inventor has found that the above problem can be solved by using an emulsion containing a specific modified polyolefin modified with an unsaturated silane compound as a sizing agent. It came.

That is, the gist of the present invention is the following [1] to [6].
[1] An emulsion containing a silane-modified polyolefin resin as a solid content in a liquid, the silane-modified polyolefin resin being a polyolefin resin grafted with 0.5 to 10% by weight of an unsaturated silane compound, and the silane An emulsion, wherein the modified polyolefin resin has a weight average molecular weight (Mw) of 50,000 to 300,000 and a flexural modulus based on JIS K7171 (1994) of 1200 MPa to 3000 MPa.
[2] In [1], the unsaturated silane compound is represented by the general formula RSi (R ′) ₃ (wherein R is an ethylenically unsaturated hydrocarbon group, R ′ is a hydrocarbon group or an alkoxy group independently of each other; At least one of which is an alkoxy group).

[3] A glass fiber sizing agent comprising the emulsion according to [1] or [2].
[4] A resin-coated glass fiber obtained by coating the glass fiber with the emulsion according to [1] or [2] and drying, wherein the emulsion has a solid content of 0.1 in the total amount of the resin-coated glass fiber. Resin-coated glass fiber coated up to 2.0% by weight.
[5] A glass fiber reinforced polyolefin resin composition containing the resin-coated glass fiber according to [4] and a polyolefin resin.
[6] The glass fiber reinforced polyolefin resin composition further containing a silane-modified polyolefin resin in [5].

According to the present invention, glass excellent in adhesiveness and sizing property with glass fiber, capable of improving the adhesiveness between glass fiber and polyolefin resin, and capable of improving the mechanical strength of glass fiber reinforced polyolefin resin. A sizing agent for fibers is provided.
Moreover, according to this invention, the glass fiber which is excellent in bundling property, is excellent in adhesiveness with polyolefin resin, and can improve the mechanical strength of glass fiber reinforced polyolefin resin is provided.
Moreover, according to this invention, the glass fiber reinforced polyolefin resin excellent in mechanical strength is provided.

  Hereinafter, the present invention will be described in detail, but the present invention is not limited to the following description, and can be arbitrarily modified and implemented without departing from the gist of the present invention.

<Silane modified polyolefin resin>
In the present invention, the silane-modified polyolefin resin is obtained by grafting a polyolefin resin with an unsaturated silane compound. Here, “grafted with an unsaturated silane compound” means that the unsaturated silane compound is not used in advance as a copolymerization component of the polyolefin resin, but is produced by reacting an unsaturated silane compound with a reaction to an already produced polyolefin resin. It is to be combined. That is, in the present invention, “graft” includes not only the case where the silane compound is introduced as a side chain having a long molecular chain length, but also the case where the unsaturated silane compound is chemically bonded to the polyolefin resin.
Compared to a polyolefin resin copolymerized with an unsaturated silane compound, grafting the unsaturated silane compound to the polyolefin resin by reaction has the advantage of a faster reaction rate with the glass surface. This is because the graft bond has a longer distance from the polyolefin main chain to the silane functional group, and the molecular motion of the silane functional group portion is easier. In other words, the molecular motion of the polyolefin main chain is constrained by the entanglement of the main chains, but the molecular motion of the graft portion is free without being constrained by the entanglement of the main chains.

In the silane-modified polyolefin resin in the present invention, the amount of modification of the unsaturated silane compound is 0.5% by weight or more, preferably 0.8% by weight or more, more preferably 1.0% by weight or more, and 10% by weight or less. , Preferably 5% by weight or less, more preferably 3% by weight or less. If the amount of modification of the unsaturated silane compound with respect to the polyolefin resin is less than the lower limit value or exceeds the upper limit value, the performance as a glass fiber sizing agent is lowered, which is not preferable.
The amount of modification of the unsaturated silane compound is confirmed by the ICI emission analysis method using a high-frequency plasma emission spectrometer, by ashing the sample by heating and burning, ash content is alkali-melted and dissolved in pure water, and then dissolved. be able to.

  Since the emulsion of the present invention described later or the sizing agent for glass fiber of the present invention uses a polyolefin substantially modified with alkoxysilane as a solid content, it has high adhesion to glass fiber and sizing property of glass fiber. The mechanical strength of the glass fiber reinforced polyolefin resin composition obtained by using this also increases. This is because the solid content of the emulsion used as the glass fiber sizing agent directly reacts with the glass surface to form a strong and hard interface, and the strain stress increases.

(A) Polyolefin resin The polyolefin resin used as a raw material for the silane-modified polyolefin resin is not limited as long as it is a polyolefin resin that can be modified with an unsaturated silane compound described later. For example, ethylene, propylene, 1-butene, etc. Homopolymers of α-olefins having 2 to 8 carbon atoms, those α-olefins or those α-olefins and 3-methyl-1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene And other α-olefins having about 2 to 20 carbon atoms such as 1-octene and 1-decene, copolymers with vinyl acetate, vinyl alcohol, (meth) acrylic acid, (meth) acrylic acid ester, etc. Can be mentioned.

Specific examples of the polyolefin resin include, for example, low, medium and high density polyethylene (branched or linear) ethylene homopolymer, ethylene-propylene copolymer, ethylene-1-butene copolymer, ethylene- 4-methyl-1-pentene copolymer, ethylene-1-hexene copolymer, ethylene-1-octene copolymer, ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer, ethylene- Ethylene resins such as (meth) acrylic acid ester copolymers; propylene resins such as propylene homopolymers, propylene-ethylene copolymers, propylene-ethylene-1-butene copolymers; and 1-butene homopolymers 1-butene resins such as 1-butene-ethylene copolymer and 1-butene-propylene copolymer; ring-opening metathesis weight of norbornene Body or norbornene derivatives - such as so-called cyclic polyolefin resins such as ethylene copolymers.
Here, the ethylene-based resin means a polymer containing ethylene as a main component as a raw material monomer, and preferably containing 50 mol% or more of ethylene. The propylene resin means a polymer containing propylene as a main component as a raw material monomer, and preferably containing 50 mol% or more of propylene. The same applies to 1-butene resins.
Especially, in this invention, the propylene-type resin used suitably for the glass fiber reinforcement molded article is suitable. The propylene-based resin may be a homopolymer, a block copolymer, or a random copolymer, but homopolypropylene (propylene homopolymer) is particularly preferable.

  In addition, since the silane-modified polyolefin resin in the present invention is usually modified in the presence of an unsaturated silane compound and a radical generator, the molecular weight is generally lowered when a propylene-based resin is used as a raw material polyolefin. In the present invention, the molecular weight of the silane-modified polyolefin resin is preferably as large as possible. Therefore, when a propylene-based resin is used, the molecular weight before modification is preferably large, and the weight average molecular weight (Mw) measured by gel permeation chromatography is preferred. ) Is 200,000 to 700,000, preferably 300,000 to 500,000. When the Mw of the propylene-based resin is lower than the lower limit, the Mw of the silane-modified polyolefin resin is not sufficiently large, and the mechanical properties may be deteriorated.

For the same reason, the melt flow rate (MFR) measured at 230 ° C. and 21.16 N load of the propylene-based resin is preferably 0.1 g / 10 min or more, more preferably 0.3 g / 10 min or more. More preferably, it is 0.5 g / 10 min or more, preferably 30 g / 10 min or less, more preferably 20 g / 10 min or less, still more preferably 15 g / 10 min or less.
When an ethylene resin or 1-butene resin is used as the raw material polyolefin, the melt flow rate (MFR) measured at 190 ° C. and 21.16 N load is preferably 0.1 g / 10 min or more. Preferably it is 0.3 g / 10 min or more, more preferably 0.5 g / 10 min or more, preferably 30 g / 10 min or less, more preferably 20 g / 10 min or less, still more preferably 15 g / 10 min or less. It is desirable.

  Further, as will be described in detail later, when a propylene resin is used as the raw material polyolefin, it is preferable that the elastic modulus of the silane-modified polyolefin resin is high to some extent. Therefore, measurement is performed according to JIS K7171 (1994) of the propylene resin before modification. The elastic modulus is preferably 1200 MPa to 3000 MPa, more preferably in the range of 1350 MPa to 3000 MPa. If the elastic modulus of the propylene-based resin is less than the lower limit, it is difficult to increase the elastic modulus of the silane-modified polyolefin resin, and the mechanical properties may be lowered.

(B) Unsaturated silane compound Although the unsaturated silane compound used for modification is not limited, the general formula RSi (R ') ₃ (wherein R is an ethylenically unsaturated hydrocarbon group, R' is a hydrocarbon group independently of each other) Alternatively, an unsaturated silane compound represented by an alkoxy group and at least one of R ′ is an alkoxy group is preferably used.
R is desirably an ethylenically unsaturated hydrocarbon group having 2 to 10 carbon atoms, preferably 2 to 6 carbon atoms. Specific examples include a vinyl group, a propenyl group, a butenyl group, and a cyclohexenyl group.

R ′ is preferably a hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms. Any of these may be an aliphatic group, an alicyclic group, or an aromatic group, but is preferably an aliphatic group. Moreover, although any of a saturated group and an unsaturated group may be sufficient, it is preferable that it is a saturated group.
When R ′ is a hydrocarbon group, specifically, an alkyl group represented by a methyl group, an ethyl group, an isopropyl group, a t-butyl group, an n-butyl group, an i-butyl group, a phenyl group, a cyclohexyl group, or the like. Or alkoxy group such as hydroxyethyl group, β-methoxyethyl group, γ- (meth) acryloxypropyl group; β-aminoethyl group, γ-aminopropyl group, γ-glycidoxypropyl group, etc. Examples include oxygen-containing and / or nitrogen-containing hydrocarbon groups; halogen-containing groups such as chloromethyl group, β-chloroethyl group, and γ-chloropropyl group.
When R ′ is an alkoxy group, specific examples include a methoxy group, an ethoxy group, an isopropoxy group, a β-methoxyethoxy group, and a γ-glycidoxypropyltrimethoxy group.

When the unsaturated silane compound is represented by the above general formula, at least one of the three R's is an alkoxy group, but preferably two, more preferably all are alkoxy groups.
As the unsaturated silane compound, vinyltrialkoxysilane represented by vinyltrimethoxysilane, vinyltriethoxysilane, propenyltrimethoxysilane and the like is preferable. This is because a vinyl group can be modified into a polyolefin resin, and an alkoxy group can be expected to have affinity with glass fiber and, in some cases, reactivity.
These unsaturated silane compounds may be used individually by 1 type, and may use 2 or more types together.
The silane-modified polyolefin resin in the present invention may be modified by using a compound other than the unsaturated silane compound in combination as long as the effects of the present invention are not impaired. Specific examples of compounds other than unsaturated silane compounds include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, ethacrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, and isocrotonic acid. Examples thereof include acids and acid anhydrides thereof.

(C) Modification method A silane-modified polyolefin resin can be obtained by modifying the unsaturated silane compound into the polyolefin resin. There are no particular restrictions on the method of modification, and solution modification, melt modification, solid-phase modification by irradiation with electron beams or ionizing radiation, modification in a supercritical fluid, and the like are suitably used according to known methods. Among them, melt modification excellent in equipment and cost competitiveness is preferable, and melt kneading modification using an extruder excellent in continuous productivity is more preferable. Examples of the apparatus used at this time include a single screw extruder, a twin screw extruder, a Banbury mixer, and a roll mixer. Among these, a single screw extruder and a twin screw extruder excellent in continuous productivity are preferable.

  Generally, modification of an unsaturated silane compound to a polyolefin resin is performed by a graft reaction in which a carbon-hydrogen bond of the polyolefin resin is cleaved to generate a carbon radical, and an unsaturated functional group is added thereto. As a generation source of the carbon radical, in addition to the above-described electron beam and ionizing radiation, a method of increasing the temperature, or a radical generator such as an organic or inorganic peroxide can be used. In view of cost and operability, it is preferable to use an organic oxide.

Although there is no limitation in the radical generator used when manufacturing a silane modified polyolefin resin, For example, what is contained in a hydroperoxide, a dialkyl peroxide, a diacyl peroxide, a peroxyester, and a ketone peroxide group, and an azo compound Etc.
Specifically, for example, the hydroperoxide group includes cumene hydroperoxide, tertiary butyl hydroperoxide, and the like, and the dialkyl peroxide group includes dicumyl peroxide, ditertiary butyl peroxide, 2,5- Dimethyl-2,5-ditertiarybutylperoxyhexane, 2,5-dimethyl-2,5-ditertiarybutylperoxyhexyne-3, etc., and the diacyl peroxide group includes lauryl peroxide and benzoyl peroxide. Etc. are included. Similarly, the peroxyester group includes tertiary peroxyacetate, tertiary butyl peroxybenzoate, tertiary butyl peroxyisopropyl carbonate, etc., and the ketone peroxide group includes cyclohexanone peroxide, etc. Azobisisobutyronitrile, methyl azoisobutyrate and the like are included.
Of these radical generators, one or several of them may be used in combination.

As an operation of melt extrusion modification generally used, the above-mentioned polyolefin resin, unsaturated silane compound, organic peroxide are blended, blended, put into a kneader, an extruder, and extruded while being heated and melt-kneaded. The molten resin emerging from the tip die is cooled in a water tank or the like to obtain a silane-modified polyolefin resin.
Although there is no restriction | limiting in particular in the mixing | blending ratio of polyolefin resin and an unsaturated silane compound, As a preferable mixing | blending range, an unsaturated silane compound is 1-20 weight part with respect to 100 weight part of polyolefin resin. If the amount of the unsaturated silane compound is too small relative to the polyolefin resin, the predetermined amount of modification necessary for obtaining the effects of the present invention may not be obtained. If the amount is too large, a large amount of the unreacted unsaturated silane compound may be obtained. Residually, there is a possibility of adversely affecting the mechanical properties of the glass fiber reinforced polyolefin resin composition.

Although there is no restriction | limiting in particular as a mixing | blending ratio of an unsaturated silane compound and an organic peroxide, As a preferable mixing | blending range, an organic peroxide is 20-100 weight part with respect to 100 weight part of unsaturated silane compounds. is there. If the amount of the organic peroxide is too small relative to the unsaturated silane compound, the predetermined amount of modification necessary for achieving the effects of the present invention cannot be obtained, and if too large, the polyolefin deteriorates and the fluidity is low. The possibility of significant deterioration arises.
Moreover, as melt-extrusion modification | denaturation conditions, it is preferable to extrude at the temperature of about 150-300 degreeC, for example in a single screw and a twin screw extruder.

(D) Other components In addition to the polyolefin resin, unsaturated silane compound, and radical generator, the silane-modified polyolefin resin in the present invention contains, as other components, a compounding agent commonly used in resin compositions. It can contain in the range which does not impair the effect of invention.
Examples of such a compounding agent include a heat stabilizer, an ultraviolet absorber, a light stabilizer, an antioxidant, an antistatic agent, a crystal nucleating agent, a rust inhibitor, and a pigment. Among these, it is preferable to contain an antioxidant, particularly a phenol-based, sulfur-based, or phosphorus-based antioxidant. It is preferable to contain 0.1-2 weight part of antioxidant with respect to 100 weight part of raw material polyolefin resin. Moreover, you may contain resin components and elastomer components other than polyolefin resin in the range which does not impair the effect of this invention. Examples of such resin components include polystyrene resins, polyvinyl chloride resins, polyester resins, polyamide resins, ethylene / vinyl alcohol copolymers, acrylic resins, and petroleum resins.
These other components may be blended at the time of modification with an unsaturated silane compound or after modification. Moreover, you may add at the time of manufacture of the emulsion mentioned later.

(E) Silane-modified polyolefin resin The silane-modified polyolefin in the present invention has a weight average molecular weight (Mw) measured by gel permeation chromatography of 50,000 or more, preferably 90,000 or more, and 300,000 or less. is there. When the Mw of the silane-modified polyolefin is smaller than the above value, the strength as a resin for coating the glass fiber is lowered, so that the physical properties such as impact strength and bending elastic modulus of the glass fiber reinforced polyolefin resin composition are not preferred. . Further, when Mw of the silane-modified polyolefin is larger than the above value, since impregnation into the glass fiber is difficult to proceed, various physical properties of the glass fiber reinforced polyolefin resin composition are lowered, which is not preferable.
In particular, as described above, when a propylene-based resin is used as the raw material polyolefin resin, when heat treatment is performed in the presence of a radical generator, molecular cleavage occurs and the molecular weight decreases. At this time, if the Mw is less than the above range, the mechanical strength of the fiber reinforced molded article is not sufficiently high, and if it is higher than the above range, emulsification is difficult and the focusing power of the glass fiber is reduced, which is not preferable. .

  The flexural modulus of the silane-modified polyolefin is 1200 MPa or more, more preferably 1500 MPa or more, still more preferably 1600 MPa or more, and 3000 MPa or less. When the flexural modulus is lower than the above range, the mechanical strength of the fiber reinforced molded product is not sufficiently high, and those higher than the above range are substantially difficult to realize in polypropylene.

The silane-modified polyolefin resin in the present invention may be cross-linked by moisture, and a cross-linked silane-modified polyolefin resin can also be used. However, for easy emulsification described later, the silane-modified polyolefin resin is substantially cross-linked. Preferably not.
In addition, a commercial item can also be used for the silane modified polyolefin resin used for this invention, for example, the Mitsubishi Chemical Co., Ltd. brand name "Linkron" can be used conveniently.

<Emulsion>
The emulsion of the present invention is a dispersion containing a silane-modified polyolefin resin described later as a solid content in a liquid.
The liquid as a dispersion medium constituting the emulsion of the present invention is not limited as long as the silane-modified polyolefin resin does not dissolve, and even water or an aqueous solution such as toluene, xylene, methyl ethyl ketone, butyl acetate, dimethylformamide, etc. Although it may be an organic solvent, it is preferably water or an aqueous solution from the viewpoint of economy, working environment, and ease of handling. In addition, when using aqueous solution as a dispersion medium, a mixed solution with water-soluble organic solvents, such as water-soluble alcohol, may be sufficient.

  The content of the silane-modified polyolefin resin in the emulsion is not limited, but it is usually 0.1% by weight or more, preferably 0.2% by weight or more, more preferably 0.5% by weight or more, and usually 10% by weight as the solid content. % Or less, preferably 5% by weight or less, more preferably 3% by weight or less. When the content of the silane-modified polyolefin resin in the emulsion is less than the above lower limit value, the convergence force is insufficient, and there is a tendency for the injuries to be worse. Glass fiber tends to block easily.

The emulsion of the present invention can be obtained by emulsifying the silane-modified polyolefin resin by a known method.
Examples of the emulsification method include a direct method and an indirect method, and any of them can be adopted. In the direct method, a modified polyolefin resin, a dispersion medium such as water, a surfactant used as necessary and other neutralizing bases are added to a container to produce an emulsified mixture. The emulsified mixture is then heated to the desired emulsification temperature. The temperature of the emulsified mixture is generally higher than the melting point of the modified polyolefin, specifically about 140 to about 185 ° C., preferably 165 to 180 ° C., but the optimum temperature depends on the melting point of the silane-modified polyolefin resin used. Strongly dependent.
In the case of an organic solvent emulsion (dispersion), it can be obtained by the same method as described above, or by dissolving and stirring the silane-modified polyolefin resin in a heated organic solvent and then cooling.

The advantage of the direct method is that it is not necessary to charge the container with pressure. Furthermore, it is a simple method that eliminates the additional steps that increase the cost of producing emulsions containing silane-modified polyolefins.
In the indirect method, first, the silane-modified polyolefin resin and a portion of at least one other component are heated above the melting point of the silane-modified polyolefin. The remaining emulsion components including the dispersion medium are then added in any order or together at an elevated temperature.

  A continuous method can also be adopted for the production of the emulsion in the present invention. As a continuous emulsion polymerization method, a method using a tubular reactor, a continuous tank reactor, a loop reactor or the like has been conventionally known. Here, the continuous emulsion polymerization method using a tubular reactor is an emulsion polymerization in a reaction tube while continuously flowing a polymer raw material liquid containing a monomer into a reaction tube having a uniform passage cross section and an inner diameter. It is a method to perform. The continuous emulsion polymerization method using a continuous tank reactor is to connect reaction tanks having stirring means in multiple stages in series, sequentially supply polymer raw material liquid to each reaction tank, and sequentially emulsion polymerization in each reaction tank. It is a method to perform. The continuous emulsion polymerization method using a loop reactor is a method in which a polymer raw material liquid is continuously supplied to a loop-shaped reaction tube and emulsion polymerization is performed while the polymer raw material liquid is circulated in the reaction tube. And a method of guiding the reaction solution containing the polymer out of the reaction tube. Any of these methods can be employed in the present invention.

The surfactant used for emulsification is not limited, and conventionally known surfactants such as cationic surfactants, anionic surfactants, amphoteric surfactants and nonionic surfactants can be used. .
Specific examples of the cationic surfactant include alkyltrimethylammonium salts represented by RN ⁺ (CHCH ₃ ) ₃ X ⁻ , dialkyldimethylammonium salts represented by RR′N ⁺ (CH ₃ ) ₂ X ⁻ , RN ⁺ ( _{CH 2 Ph) (CH 3)} 2 X - include alkyl benzyl dimethyl ammonium salts represented by specific examples of anionic surface active agents, ^RCOO - sodium fatty acid represented by Na ⁺ (soaps), ROSO ₃ ^- monoalkyl sulfates represented by _{^{M +, RO (CH 2 CH}} 2 O) m SO 3 - alkyl polyoxyethylene sulfates represented by _{^{M +, RR'CH 2 CHC 6 H}} 4 SO 3 - represented by M ⁺ Alkylbenzenesulfonates, monoalkylphosphates represented by ROPO (OH) O ^- M ⁺ Specific examples of amphoteric surfactants include alkyldimethylamine oxides represented by R (CH ₃ ) ₂ NO, alkyl carboxybetaines represented by R (CH ₃ ) ₂ N ⁺ CH ₂ COO ⁻ , and the like Specific examples of the nonionic surfactant include polyoxyethylene alkyl ethers represented by RO (CH ₂ CH ₂ O) _m H, fatty acid diethanolamide represented by RCON (CH ₂ CH ₂ OH) ₂ And alkyl monoglyceryl ethers represented by OCH ₂ CH (OH) CH ₂ OH, fatty acid sorbitan esters, alkyl polyglucosides, and the like. Two or more of these can be used in combination as long as the effect is not impaired.

Although the addition amount of surfactant is not limited, 1-30 weight part with respect to 100 weight part of silane modified polyolefin resin, Preferably 10-20 weight part is suitable.
When the emulsion of the present invention is coated on glass, the solid content mainly composed of a silane-modified polyolefin resin is excellent in affinity and adhesion to glass, and is particularly excellent as a sizing agent for glass fibers.

<Bundling agent for glass fiber>
The emulsion of the present invention exhibits good sizing properties when applied to glass fibers and dried. Therefore, the sizing agent for glass fibers of the present invention may be the emulsion itself of the present invention.
The use of the emulsion containing the silane-modified polyolefin resin of the present invention as a glass fiber sizing agent has the advantage that the strength of the glass fiber reinforced polyolefin resin composition is improved as compared with the case of using a known silane coupling agent. is there. This is because the silane coupling agent has no crystallinity (or very low), whereas the silane-modified polyolefin resin has crystallinity, so that an improvement in cohesion can be expected.
In addition, since the glass fiber sizing agent of the present invention is characterized by having a structure capable of silane coupling, it is not necessary to use the silane coupling agent normally used for the sizing agent. Depending on the case, a silane coupling agent may be used.

The silane coupling agent that can be used is not limited, but γ-aminopropyltriethoxysilane, γ-ureidopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropyl. One or more silane coupling agents selected from trimethoxysilane, N- (β-aminoethyl) -γ-amino30propylmethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane and the like Can be used. Moreover, when using a silane coupling agent, the thing containing 0.1 to 1 weight% with respect to solid content of an emulsion, desirably 0.3 to 0.8 weight% can be used conveniently. When a silane coupling agent is used, the silane coupling agent may be contained in the emulsion or may be coated on the surface of the glass fiber in advance, but the inclusion in the emulsion is preferred.
Further, the glass fiber sizing agent of the present invention contains components such as a binder such as urethane resin, acrylic resin, and epoxy resin, a lubricant, an antistatic agent, etc., in addition to the above-described components. Can be added.

<Resin-coated glass fiber>
The resin-coated glass fiber of the present invention means a glass fiber coated with at least the above-mentioned silane-modified polyolefin resin, but more specifically means a glass fiber focused by the glass fiber sizing agent of the present invention.
The shape of the resin-coated glass fiber is not limited, and may be cut into chopped strands (short fibers) or may be continuous roving (long fibers) without being cut.
Although the glass fiber processed by the said glass fiber sizing agent in this invention is not limited, It is preferable that the average diameter of a monofilament is 6-23 micrometers, More preferably, it is 10-17 micrometers. If the average diameter of the monofilament is less than the lower limit, the pellet becomes expensive because the number of glass fibers required to exhibit the same characteristics increases when the pellet is impregnated with a matrix resin later. When the upper limit is exceeded, the mechanical properties of the pellets tend to be inferior.

The number of bundles of the resin-coated glass fibers of the present invention by the sizing agent is not limited, but in the case of monofilament, it is usually 100 or more, preferably 1000 or more, and usually 7000 or less, preferably 4000 or less. When the number of chopped strands is less than the lower limit, glass fibers tend to fluff and tend to break when opened by protrusions or rollers, and when the number of bundles exceeds the upper limit, the polyolefin resin is impregnated. Is insufficient, and physical properties such as bending strength tend to decrease.
In the continuous roving, the number of focused beams is usually 400 or more, preferably 1000 or more, and usually 40000 or less, preferably 10,000 or less. If the number of continuous rovings is less than the lower limit, the fluidity tends to deteriorate and the molding tends to be poor.If the number of continuous rovings exceeds the upper limit, the polyolefin resin is not sufficiently impregnated, such as bending strength. The physical properties tend to decrease.

  When the resin-coated glass fibers of the present invention are chopped strands, the average fiber length is not limited, but is usually 1 mm or more, preferably 3 mm or more, and usually 20 mm or less, preferably 10 mm or less. When the average fiber length of the chopped strand is less than the lower limit, the residual average fiber length in the glass fiber reinforced polyolefin resin composition is shortened, so that the physical properties such as bending strength tend to decrease, and the average fiber length is When the upper limit is exceeded, the residual average fiber length in the glass fiber reinforced polyolefin resin composition does not change substantially, but the handling during blending with the polyolefin resin or the like tends to deteriorate.

In the resin-coated glass fiber of the present invention, the solid content of the glass fiber sizing agent with respect to the glass fiber is not limited, but is usually 0.1% by weight or more, preferably 0.3% by weight or more, usually 3% by weight or less, Is 2% by weight or less. When the solid content is less than the lower limit, the fiber is not sufficiently converged and easily fuzzed, and the adhesion between the fiber and the matrix resin tends to be inferior. On the other hand, when the solid content exceeds the upper limit, the matrix resin is formed. In some cases, the fiber bundles are not sufficiently defibrated at the time of impregnation, and a defect due to the presence of undefibrated fiber bundles in the matrix resin may occur.
In addition, it does not specifically limit about the processing method of the glass fiber by the glass fiber sizing agent of this invention, Any well-known processing method may be sufficient.

<Glass fiber reinforced polyolefin resin composition>
The glass fiber reinforced polyolefin resin composition of the present invention means a polyolefin resin composition containing the resin-coated glass fiber of the present invention. That is, it is a composition containing at least the resin-coated glass fiber of the present invention and a polyolefin resin. By impregnating glass fibers into a polyolefin resin, a resin composition having excellent mechanical properties and heat resistance can be obtained.

The resin-coated glass fiber may be a chopped strand (short fiber) or continuous roving (long fiber). The former is called a short fiber reinforced polyolefin resin composition, and the latter is used. This was called a long fiber reinforced polyolefin resin composition.
As the polyolefin resin, any selected from the above polyolefin resins that can be used as a raw material of the silane-modified polyolefin resin can be used. Two or more of these polyolefin resins may be used in combination. Among these polyolefin resins, in the present invention, in view of extrudability of the resin, moldability, various properties of the obtained resin composition, and the like, those mainly composed of an ethylene-based resin or a propylene-based resin are preferable. Particularly preferred is a propylene resin.

  The glass fiber reinforced polyolefin resin composition of the present invention preferably uses the silane-modified polyolefin resin of the present invention in combination with the polyolefin resin. By using the silane-modified polyolefin resin in combination with the polyolefin resin, the reinforcing effect of the resin-coated glass fiber can be synergistically increased, and the mechanical strength of the molded product is dramatically improved. Two or more silane-modified polyolefin resins can be used in combination. The amount used when the silane-modified polyolefin resin is used in combination with the polyolefin resin is not limited, but in the glass fiber reinforced polyolefin resin composition, the silane-modified polyolefin resin is preferably used in a proportion of 0.5 to 10% by weight, A ratio of 2 to 8% by weight is more preferable. When the ratio of the silane-modified polyolefin resin in the fiber-reinforced polyolefin resin composition is lower than the lower limit, the strength tends not to be sufficiently improved, and when it is higher than the upper limit, the strength tends to decrease. is there. This is because the molecular weight of the silane-modified polyolefin resin is lower than that of the matrix resin and the mechanical strength is low.

In the present invention, when a polyolefin resin and a silane-modified polyolefin resin are used in combination as the matrix resin, it is preferable that the main resin constituent units are the same. A specific example is a combination of polypropylene and silane-modified polypropylene.
In addition, the glass fiber reinforced polyolefin resin composition of the present invention can be supplementarily used in combination with one or more other thermoplastic resins as long as the purpose and effect thereof are not significantly impaired. In addition, in order to impart desired properties according to the purpose, known substances generally added to thermoplastic resins, for example, antioxidants, heat stabilizers, stabilizers such as ultraviolet absorbers, antistatic agents, flame retardants, Flame retardant aids, colorants such as dyes and pigments, lubricants, plasticizers, crystallization accelerators, crystal nucleating agents, and the like can be further blended. Further, glassy flakes, mica, glass powder, glass beads, talc, clay, alumina, carbon black, wollastonite and other plate-like or powdery inorganic compounds, whiskers and the like may be used in combination.

<Short fiber reinforced polyolefin resin composition>
The production method of the short fiber reinforced polyolefin resin composition is not particularly limited, and any known method can be suitably used, but it is particularly preferable to use a melt-kneading method excellent in productivity and cost.
In the case of the melt-kneading method, the matrix resin is melted with a twin screw extruder, and resin-coated glass fibers are introduced through a feed port in the middle, and the resin and resin-coated glass fibers pre-blended with a twin screw or single screw extruder There is a method of melting and kneading. Although continuous roving can be used as the form of the resin-coated glass fiber, chopped strands are preferably used. Even when continuous roving is used, since shearing is applied by a kneader, most of the glass fibers are broken and the remaining fiber length is generally 2 mm or less.

<Long fiber reinforced polyolefin resin composition>
In general, the long fiber reinforced polyolefin resin composition is obtained by treating glass fibers with the above-described sizing agent for glass fibers to form continuous roving and impregnating the fiber bundle with the polyolefin resin. The impregnation method is not limited, but the pultrusion method is preferable.
In the pultrusion method, the continuous roving is basically impregnated with a polyolefin resin while drawing the continuous roving. Specifically, a method of impregnating a matrix resin through continuous roving in an impregnation bath containing a polyolefin resin emulsion, suspension or solution as a matrix, or spraying a polyolefin resin powder onto a continuous roving or putting a powder A method in which continuous roving is passed through the tank, polyolefin resin powder is adhered to the glass fiber, and then the polyolefin resin is melted and impregnated in the continuous roving. Examples include a method of supplying a polyolefin resin to the fiber and impregnating the fiber bundle, and any method can be used. Particularly preferred is a method using a crosshead.

  In addition, the polyolefin resin impregnation operation in the pultrusion molding is generally performed in one stage, but it may be performed in two or more stages. That is, as a polyolefin resin to be impregnated in continuous roving, when a polyolefin resin and a silane-modified polyolefin resin are used in combination, a method of impregnation by a one-stage impregnation operation using a melt obtained by mixing these in a predetermined ratio, an impregnation operation In each impregnation step, the fiber bundle can be impregnated with a matrix resin having an arbitrary ratio of polyolefin resin and silane-modified polyolefin resin, and finally a desired resin composition can be used. It is.

  Further, when the glass fiber reinforced polyolefin resin composition of the present invention is a long fiber reinforced polyolefin resin composition, the glass fiber has a length of substantially 2 mm or more, preferably 5 mm or more, more preferably 10 mm or more, And it is preferable to arrange in a state substantially parallel to each other. When the fiber length is less than the lower limit, when such a resin composition is molded, there is a tendency that sufficient strength cannot be expected in the molded product. In particular, the long fiber reinforced polyolefin resin composition is in the form of a pellet having a length of 2 to 50 mm in order to obtain a molded product that has excellent strength without impairing the injection moldability, and subjected to injection molding that is easy to perform the molding process. It is preferable to use a wire-like composition in which the fibers are arranged in substantially the same length as the pellet.

The blending amount of the resin-coated glass fiber in the glass fiber reinforced polyolefin resin composition is not limited, but it is 5% by weight or more, preferably 10% by weight or more, more preferably 20% by weight or more in the resin composition, usually 80%. % By weight or less, preferably 70% by weight or less, more preferably 65% by weight or less. When the blending amount of the resin-coated glass fiber is less than the lower limit value, the reinforcing effect of the polyolefin resin by the glass fiber is small. Further, further improvement in strength due to an increase in the amount of fibers can hardly be expected.

In the method for producing the short fiber reinforced polyolefin resin composition or the long fiber reinforced polyolefin resin composition, the temperature of the polyolefin resin for impregnating the glass fiber is not limited, but is preferably set to 180 to 320 ° C. The above temperature is particularly preferable when using a propylene resin as a main component.
The shape of the glass fiber reinforced polyolefin resin composition of the present invention obtained as described above is not limited, and any shape such as a strand shape, a sheet shape, a flat plate shape, or a pellet shape obtained by cutting a strand into an appropriate length can be used. Is possible. In particular, a wire-like composition having a length of 2 to 50 mm is preferable for application to injection molding, which is easy to mold. Moreover, in the case of a long fiber reinforced polyolefin resin composition, it is preferable to use a molded product in which glass fibers in a molded product as a final product are dispersed with a mass average fiber length of 1 mm or more. Thereby, it can be set as the molded article holding high mechanical strength.
The glass fiber reinforced polyolefin resin composition obtained by the present invention can be formed into an arbitrary molded body by various known molding methods. Among these, it is preferable to perform injection molding excellent in molding processability.

<Application>
The molded product produced from the glass fiber reinforced polyolefin resin composition of the present invention has drastically improved mechanical strength and heat resistance, and can retain high reliability.
Although the use of the glass fiber reinforced polyolefin resin composition of the present invention is not limited, automobile parts (front end, fan sheroud, cooling fan, engine under cover, engine cover, radiator box, side door, back door inner, back door outer, Outer panels, roof rails, door handles, luggage boxes, wheel covers, handles, cooling modules, air cleaner parts, air cleaner cases, pedals, motorcycle and bicycle parts (luggage boxes, handles, wheels), housing-related parts (hot water wash valves) Seat parts, bathroom parts, chair legs, valves, meter boxes, etc. (washing machine parts and washing / drying machine parts (balance ring, dehydration receptacle cover, dehydration receptacle, exhaust outlet guide, etc.), electric tool parts, mower hand , Hose joint, useful for making the product of the resin bolts, concrete form). It is especially suitable for manufacturing automobile parts such as luggage boxes, side doors, air cleaner cases, back door inners, front end modules (including fan sherouds, fans, cooling modules), meter boxes, switchboards, and engine covers.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist.
In the examples and comparative examples of the present invention, the following raw materials and measurement methods were used.

<Polyolefin resin>
PO-1: Novatec PP EA9 (Nippon Polypro, Homopolypropylene, MFR = 0.5 g / 10 min (230 ° C., 21.16 N load), flexural modulus = 1800 MPa)
PO-2: Novatec PP MA3 (Nippon Polypro, Homopolypropylene, MFR = 11 g / 10 min (230 ° C., 21.16 N load), flexural modulus = 1500 MPa)
PO-3: Novatec PP MG2T (Nippon Polypro, Homopolypropylene, MFR = 15 g / 10 min (230 ° C., 21.16 N load), flexural modulus = 1350 MPa
)
PO-4: Novatec PP MA3H (Homopolypropylene manufactured by Nippon Polypro, M
FR = 10 g / 10 min (230 ° C., 21.16 N load), flexural modulus = 2000 MPa)
PO-5: Novatec PP EG8 (Nippon Polypro Random Polypropylene, MFR = 0.8 g / 10 min (230 ° C., 21.16 N load), flexural modulus = 1150 MPa)

<Measurement method>
・ Silane modification amount: Silane-modified polyolefin resin is incinerated by heating and ashing, ash is melted with alkali, dissolved in pure water and then dissolved, and ICI emission analysis using a high-frequency plasma emission spectrometer (ICPS7510 manufactured by Shimadzu Corporation). The amount of silane was determined by
-Tensile fracture strength: Measured according to the method described in JIS-K7113 (1994).
Flexural strength and flexural modulus: Measured according to the method described in JIS-K7171 (1994).
-Izod impact strength: Measured according to the method described in JIS-K7110 (1994).
Heat distortion temperature: Measured under conditions of stress 0.45 MPa according to the method described in ASTM-D-648.
-Solid content adhesion amount of bundling agent in chopped strand and continuous roving: 10 g of chopped strand or cut continuous roving was placed in a magnetic crucible and baked at 600 ° C for 3 hours in an electric furnace. After firing, the magnetic crucible was allowed to cool to room temperature in a dry desiccator. The weight of the glass fiber was measured, and the reduced amount was calculated as the sizing agent adhesion amount (% by weight).

[Example 1]
As a polyolefin resin, 2 parts by weight of vinyltrimethoxysilane (VTMOS) and 0.4 parts by weight of dicumyl peroxide are stirred in a blender with respect to 100 parts by weight of PO-1, and the temperature is set to 220 ° C. It put into the granulator (Ikegai company make, PCM45), and after cooling and solidifying the strand which came out of the nozzle in the water tank, it cut into the pellet form, and obtained the silane modified polyolefin resin (SPP-1). Table 1 shows the silane modification amount, weight average molecular weight, and flexural modulus of SPP-1.
Next, a sizing agent was prepared as an emulsion (4.0 wt% based on solid content, 96.0 wt% deionized water) emulsified using SPP-1 as a film forming component. The sizing agent was prepared by adding 30 g of SPP-1, 0.06 g of sodium hydroxide, 0.75 g of polypropylene glycol, 0.25 g of sorbitan monostearate, and 70 g of deionized water in a 200 mL autoclave equipped with a stirrer. Then, this mixture is heated at 175 ° C. for 0.5 hours with high-speed stirring, and then allowed to cool to room temperature with stirring, and the emulsion (solid content concentration of about 30% by weight) is diluted in deionized water. I got it.

Thereafter, the obtained sizing agent was applied to the surface of glass fibers having an average fiber diameter of 16 μm, and about 2200 glass fibers were bundled into strands, cut into 2 mm lengths and dried to obtain glass chopped strands. . The solid content of the sizing agent in the obtained chopped strand was 1.0% by weight.
Next, 65% by weight of PO-2 as polyolefin resin, 5% by weight of SPP-1, and 30% by weight of the chopped strand were kneaded in a twin-screw extruder while being heated at 240 ° C., and then pelletized. A glass fiber reinforced polyolefin molded article was produced by injection molding the pellet. Table 2 shows the physical properties of the obtained glass fiber reinforced polyolefin molded article.

[Example 2]
As polyolefin resin, in addition to 3.0 parts by weight of VTMOS and 1.0 part by weight of dicumyl peroxide with respect to 100 parts by weight of PO-3, as a crystal nucleating agent, IRGA manufactured by IRSF
After stirring 0.1 parts by weight of STAB NA11 (trade name) with a blender, a silane-modified polyolefin resin (SPP-2) was obtained in the same manner as in Example 1. Table 1 shows the silane modification amount, weight average molecular weight, and flexural modulus of SPP-2.
Next, a sizing agent was prepared in the same manner as in Example 1 using SPP-2, and chopped strands were obtained in the same manner as in Example 1. The solid content of the sizing agent to the obtained chopped strand was 1.0% by weight.
Next, a glass fiber reinforced polyolefin molded article was produced in the same manner as in Example 1 except that 60% by weight of PO-2, 10% by weight of SPP-2, and 30% by weight of the chopped strand were used as the polyolefin resin. Table 2 shows the physical properties of the obtained glass fiber reinforced polyolefin molded article.

[Example 3]
As a polyolefin resin, 100 parts by weight of PO-1 and 2 parts by weight of vinyltriethoxysilane (VTEOS) and 0.5 parts by weight of dicumyl peroxide were stirred in a blender, and the silane-modified polyolefin was treated in the same manner as in Example 1. Resin (SPP-3) was obtained. Table 1 shows the silane modification amount, weight average molecular weight, and flexural modulus of SPP-3.
Next, a sizing agent was prepared using SPP-3 in the same manner as in Example 1, and this sizing agent was applied to the surface of a glass fiber having an average fiber diameter of 16 μm, and about 2200 glass fibers were focused to perform continuous roving. did. The solid content of the sizing agent on the obtained roving was 1.0% by weight.
Next, while pulling the continuous roving through the crosshead processed into a corrugated passage, SPP-3 is added to 100 parts by weight of polyolefin resin (PO-2) supplied at 250 ° C. from an extruder connected to the crosshead. After impregnating the molten mixture in an amount of 10 parts by weight, the mixture was taken up as a strand through a shaping die, and a pellet-like composition having a glass fiber content of 40% by weight and a length of 12 mm was obtained. The obtained pellets were injection molded to produce a glass fiber reinforced polyolefin molded product. Table 2 shows the physical properties of the glass fiber reinforced polyolefin molded article.

[Example 4]
As a polyolefin resin, 7 parts by weight of VTEOS and 1.2 parts by weight of dicumyl peroxide were stirred with a blender with respect to 100 parts by weight of PO-4, and then a silane-modified polyolefin resin (SPP-4) in the same manner as in Example 1. Got. Table 1 shows the silane modification amount, weight average molecular weight, and flexural modulus of SPP-4.
Next, a sizing agent was prepared in the same manner as in Example 1 using SPP-4, and chopped strands were obtained in the same manner as in Example 1. The solid content of the sizing agent to the obtained chopped strand was 1.0% by weight.
Next, a glass fiber reinforced polyolefin molded article was produced in the same manner as in Example 1 except that the chopped strand was used and SPP-4 was used instead of SPP-1. Table 2 shows the physical properties of the obtained glass fiber reinforced polyolefin molded article.

[Example 5]
As a polyolefin resin, 1.0 part by weight of VTMOS and 0.2 part by weight of dicumyl peroxide were stirred with a blender with respect to 100 parts by weight of PO-1, and then a silane-modified polyolefin resin (SPP- 5) was obtained. Table 1 shows the silane modification amount, weight average molecular weight, and flexural modulus of SPP-5.
Next, chopped strands were obtained in the same manner as in Example 1 using SPP-5. The solid content of the sizing agent to the obtained chopped strand was 1.0% by weight.
Next, a glass fiber reinforced polyolefin molded article was produced in the same manner as in Example 1 except that the chopped strand was used and SPP-5 was used instead of SPP-1. Table 2 shows the physical properties of the obtained glass fiber reinforced polyolefin molded article.

[Example 6]
As a polyolefin resin, 100 parts by weight of PO-1 and 2 parts by weight of VTMOS, 0.5 parts by weight of dicumyl peroxide, and 0.1 parts by weight of IRGASTAB NA11 (trade name) manufactured by BASF as a crystal nucleating agent are stirred in a blender. Thereafter, a silane-modified polyolefin resin (SPP-6) was obtained in the same manner as in Example 1. Table 1 shows the silane modification amount, weight average molecular weight, and flexural modulus of SPP-6.
Next, using SPP-6 as a film forming component, a sizing agent was prepared which was emulsified by the same method as in Example 1 (6.0 wt% based on solid content, 94.0 wt% deionized water). .
Thereafter, a glass chopped strand was obtained in the same manner as in Example 1. The solid content of the sizing agent to the obtained chopped strand was 1.5% by weight.
Using this chopped strand, a glass fiber reinforced polyolefin molded article was produced in the same manner as in Example 1 except that SPP-6 was used instead of SPP-1. Table 2 shows the physical properties of the obtained glass fiber reinforced polyolefin molded article.

[Example 7]
Using SPP-1 as a film-forming component, a sizing agent was prepared that was emulsified in the same manner as in Example 1 (2.0% by weight on a solid basis, 98.0% by weight of deionized water).
Thereafter, a glass chopped strand was obtained in the same manner as in Example 1. The solid content of the sizing agent on the obtained chopped strand was 0.5% by weight.
A glass fiber reinforced polyolefin molded article was produced in the same manner as in Example 1 except that this chopped strand was used. Table 2 shows the physical properties of the obtained glass fiber reinforced polyolefin molded article.

[Comparative Example 1]
A modified polyolefin resin (MPP-1) was obtained in the same manner as in Example 1 except that maleic anhydride (MAH) was used as a modifying component instead of using an unsaturated silane compound (VTMOS). Table 1 shows the weight average molecular weight and flexural modulus of MPP-1. The modification amount of MAH was 1% by weight as measured by NMR method.
Next, a glass chopped strand was obtained in the same manner as in Example 1 except that MPP-1 was used. The solid content of the sizing agent to the obtained chopped strand was 1.0% by weight.
A glass fiber reinforced polyolefin resin molded article was produced in the same manner as in Example 1 except that this chopped strand was used. Table 3 shows the physical properties of the obtained glass fiber reinforced polyolefin molded article.

[Comparative Example 2]
A continuous roving was obtained in the same manner as in Example 3 except that MPP-1 was used instead of SPP-3, and a glass fiber reinforced polyolefin molded article was produced in the same manner as in Example 3. Table 3 shows the physical properties of the obtained glass fiber reinforced polyolefin molded article.

[Comparative Example 3]
A silane-modified polyolefin resin (SPP-7) was obtained in the same manner as in Example 1 except that PO-5 was used as the polyolefin resin. Table 1 shows the silane modification amount, weight average molecular weight, and flexural modulus of SPP-7.
Next, a sizing agent was prepared using SPP-7 in the same manner as in Example 1, and a glass chopped strand was obtained in the same manner as in Example 1. The solid content of the sizing agent to the obtained chopped strand was 1.0% by weight.
Using this chopped strand, a glass fiber reinforced polyolefin molded article was produced in the same manner as in Example 1. Table-shows the physical properties of the obtained glass fiber reinforced polyolefin moldings.
3 shows.

[Comparative Example 4]
A silane-modified polyolefin resin (SPP-8) was obtained in the same manner as in Example 1 except that 0.2 parts by weight of VTMOS and 0.2 parts by weight of dicumyl peroxide were used as the polyolefin resin with respect to 100 parts by weight of PO-1. It was. Table 1 shows the silane modification amount, weight average molecular weight, and flexural modulus of SPP-8.
Next, an emulsification operation was carried out in the same manner as in Example 1 except that SPP-8 was used instead of SPP-1, but an emulsion (bundling agent) could not be prepared. For this reason, operation after the coating to glass fiber was not performed.

[Comparative Example 5]
As a polyolefin resin, 100 parts by weight of PO-4, VTMOS 5.0 parts by weight, dicumyl peroxide 3.0 parts by weight were charged to Toyo Seiki Lab Plast Mill (product name), The mixture was kneaded for 10 minutes at a rotation speed of 100 rpm with nitrogen sealing to obtain a silane-modified polyolefin resin (SPP-9). Table 1 shows the silane modification amount, weight average molecular weight, and flexural modulus of SPP-9.
Next, a glass chopped strand was obtained in the same manner as in Example 1 except that SPP-9 was used instead of SPP-1. The solid content of the sizing agent to the obtained chopped strand was 1.0% by weight.
Using this chopped strand, a glass fiber reinforced polyolefin molded article was produced in the same manner as in Example 1. Table 3 shows the physical properties of the obtained glass fiber reinforced polyolefin molded article.

Claims (6)

  An emulsion containing a silane-modified polyolefin resin as a solid content in a liquid, the silane-modified polyolefin resin being a polyolefin resin grafted with 0.5 to 10% by weight of an unsaturated silane compound, and the silane-modified polyolefin resin The emulsion has a weight average molecular weight (Mw) of 50,000 to 300,000 and a flexural modulus based on JIS K7171 (1994) of 1200 MPa to 3000 MPa. The unsaturated silane compound has the general formula RSi (R ′) ₃ (wherein R is an ethylenically unsaturated hydrocarbon group, R ′ is a hydrocarbon group or an alkoxy group independently of each other, and at least one of R ′ is an alkoxy group) The emulsion according to claim 1, which is an unsaturated silane compound represented by:   A sizing agent for glass fibers comprising the emulsion according to claim 1 or 2.   A resin-coated glass fiber obtained by coating the glass fiber with the emulsion according to claim 1 or 2 and drying, wherein the emulsion is 0.1 to 2.0 weight as a solid content in the total amount of the resin-coated glass fiber. % Resin-coated glass fiber, characterized in that it is coated.   A glass fiber-reinforced polyolefin resin composition comprising the resin-coated glass fiber according to claim 4 and a polyolefin resin. The glass fiber reinforced polyolefin resin composition according to claim 5, further comprising a silane-modified polyolefin resin.