JP2003238211A - Emulsion for glass fiber sizing agent and method for producing the same, and glass fiber sizing agent, glass fiber bundle, resin composition, resin molding, and method for producing the resin molding - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a glass fiber sizing agent having excellent storage stability and sizing performance for manufacturing FRP (fiber reinforced plastic) having excellent weather resistance without causing defects in appearance or lowering physical properties and to provide a glass fiber bundle formed using the glass fiber sizing agent and having excellent suitability to cutting. <P>SOLUTION: The glass fiber sizing agent is based on an emulsion for a glass fiber sizing agent containing (meth)acrylic polymer particles and a water- soluble polymer containing a (meth)acrylamide unit. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a glass fiber sizing agent emulsion used as a constituent of a glass fiber sizing agent used for staking glass fibers, a method for producing the same, and a glass fiber sizing method using the emulsion. Agent, a glass fiber bundle formed by applying the glass fiber sizing agent, a resin composition containing the glass fiber bundle, a resin molded article, and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, glass fiber reinforced resin (hereinafter referred to as "FR
P) is excellent in strength, chemical stability and the like, and is therefore widely used in bathtubs, water storage tanks, boats, automobile parts and the like.

The FRP is usually manufactured by using a resin serving as a matrix and a glass fiber bundle (strand).
This glass fiber bundle is generally produced by bundling hundreds of glass fibers obtained through the glass fiber spinning step and treating the glass fiber bundle with a glass fiber sizing agent.

Generally, the glass fiber sizing agent is composed of a film forming agent, a surface treating agent, a lubricant, an antistatic agent and the like, and a polyvinyl acetate emulsion is often used as the main film forming agent.

For example, in JP-A-49-87888, it is obtained by emulsion polymerization of a vinyl ester such as vinyl acetate in the presence of a partially saponified polyvinyl alcohol having a saponification degree of 70 to 90 mol% and a nonionic surfactant. A glass fiber sizing agent comprising the obtained emulsion is disclosed.
It is described that this glass fiber sizing agent has good adhesiveness to glass fibers, and that the FRP plate produced using the glass fibers treated with the emulsion has excellent transparency.

[0006] The publication discloses a case where an unsaturated polyester is used as the matrix resin as the FRP. However, since the unsaturated polyester resin has low weather resistance, it has excellent weather resistance as the matrix resin for the FRP. It is desirable to use a (meth) acrylic resin that is also excellent in transparency.

However, when a (meth) acrylic resin is used as the FRP matrix resin, the compatibility of the (meth) acrylic resin with the vinyl ester polymer such as polyvinyl acetate as a sizing agent is low, and thus glass fiber is used. There is a problem in that the sizing agent is not well compatible with the matrix resin, the sizing agent is not sufficiently dissolved, or the glass fiber is not sufficiently opened. As a result, appearance defects such as embossing of fiber marks on the surface of the molded product or deterioration of physical properties of the molded product such as boiling resistance, weather resistance and mechanical properties are caused.

On the other hand, an example using a (meth) acrylic polymer as a main component of a glass fiber sizing agent or a sizing agent is disclosed in JP-A-50-30967 or JP-A-51.
-67492 gazette etc. are disclosed.

Japanese Unexamined Patent Publication No. 50-30967 discloses N-
A glass fiber sizing agent containing an acrylic polymer containing alkylol acrylamide as an essential polymerization component is disclosed. The glass fiber sizing agent disclosed in the publication is applied to a reinforcing glass fiber used in an FRP containing a thermoplastic resin such as styrene-acrylonitrile copolymer resin as a matrix resin, and particularly improves the mechanical strength of the FRP. It is described that it is possible.

However, when this glass fiber sizing agent is applied to a reinforcing glass fiber contained in a thermosetting resin composition such as a sheet molding compound or a bulk molding compound, the glass fiber does not sufficiently open, and molding is performed. The surface smoothness of the product is poor and the appearance is poor. This is because the acrylic polymer contained in the glass fiber sizing agent contains N-alkylol acrylamide, which is a self-crosslinking monomer, as an essential component, so a crosslinking reaction occurs in the coating film formed by the sizing agent, and this size This is because the agent film does not dissolve in the monomer in the composition.

Japanese Unexamined Patent Publication (Kokai) No. 51-67492 discloses a glass fiber sizing agent comprising an emulsion containing polyvinyl alcohol and a polymer containing at least 20% by mass of (meth) acrylic acid ester as a copolymerization component. ing. The sizing agent disclosed in the publication has a degree of polymerization of 5
It is described that it contains about 00 polyvinyl alcohol (water-soluble polymer of low molecular weight) and is essential for improving the focusing property, but the water absorption rate of the molded product tends to be high, and it is used as a matrix resin for FRP. Even when a (meth) acrylic resin is used, the weather resistance of the molded product is reduced.

Further, the glass fiber sizing agents or sizing agents disclosed in JP-A-50-30967 and JP-A-51-67492 have a short usable period and lack stability. These glass fiber sizing agents or sizing agents do not agglomerate immediately after the (meth) acrylic polymer is mixed with other components such as a surface treatment agent and a lubricant, but generally they easily agglomerate, and depending on the composition, it takes about 2 days. It will aggregate and become difficult to use.

Further, the glass fiber bundles treated with the glass fiber sizing agent or sizing agent disclosed in JP-A-50-30967 and JP-A-51-67492 have insufficient cutting workability. However, it also has a drawback that it is inferior in workability such that the cutting work by the cutter cannot be performed smoothly.

[0014]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to produce a glass fiber sizing agent which is capable of producing an FRP having excellent weather resistance without causing a poor appearance and deterioration of physical properties, and which is excellent in storage stability and sizing property. And an emulsion for a glass fiber sizing agent used for this sizing agent, and a glass fiber bundle formed by using this glass fiber sizing agent and having excellent cutting processability. Another object is to provide a resin molded product having good appearance and weather resistance.

[0015]

The present invention relates to an emulsion for glass fiber sizing agents containing (meth) acrylic polymer particles and a water-soluble polymer containing a (meth) acrylamide unit.

The present invention also relates to the above emulsion for glass fiber sizing agent, which is obtained by polymerizing at least a (meth) acrylic monomer in the presence of a water-soluble polymer containing a (meth) acrylamide unit.

Further, the present invention is characterized by polymerizing at least a (meth) acrylic monomer in the presence of a water-soluble polymer containing a (meth) acrylamide unit. Manufacturing method.

The present invention also relates to a glass fiber sizing agent containing the above emulsion.

The present invention also relates to a glass fiber bundle formed by applying the above glass fiber sizing agent.

The present invention also relates to a resin composition containing the above glass fiber bundle.

The present invention also relates to the above resin composition containing a (meth) acrylic resin.

The present invention also relates to the above resin composition, wherein the resin composition is a sheet molding compound.

The present invention also relates to the above resin composition, wherein the resin composition is a bulk molding compound.

The present invention also relates to a resin molded product containing the above glass fiber bundle.

The present invention also relates to the above resin molded product containing a (meth) acrylic resin as a matrix resin.

The present invention also relates to a method for producing a resin molded product, characterized in that the glass fiber bundle formed by applying the above-mentioned glass fiber sizing agent is mixed with a resin or a resin composition and molded.

In the present specification, "(meth) acrylate" means "acrylate or methacrylate, or acrylate and methacrylate".

[0028]

BEST MODE FOR CARRYING OUT THE INVENTION Preferred embodiments of the present invention will be described below.

The emulsion for a glass fiber sizing agent in the present invention is a water-soluble emulsion containing (meth) acrylic polymer particles (component (A)) and (meth) acrylamide as at least one polymerization component ((meth) acrylamide unit). It is an emulsion containing a polymer (component (B)) and can be used as a film forming agent in the constituent components of the glass fiber sizing agent.

The component (A) is obtained by homopolymerizing a (meth) acrylic monomer, or a (meth) acrylic monomer and a monomer copolymerizable with the (meth) acrylic monomer. It is a particle of a polymer formed by copolymerization and can form a film on the surface of glass fiber. The component (A) may be a cross-linked polymer or a non-cross-linked polymer, and can be appropriately selected according to desired characteristics. When the component (A) is a non-crosslinked polymer, the openability of the glass fiber bundle is improved, the number of glass fiber marks on the surface of the resin molded product is less likely to be raised, and the appearance tends to be improved. In the case of coalescence, the mechanical properties of the coating are improved, the cutting processability of the glass fiber bundle is improved, and fuzzing tends to be reduced. In particular, when used in a glass fiber bundle of FRP having a thermosetting resin as a matrix resin, it is preferable that at least a non-crosslinked polymer component is contained.

The particle structure of the component (A) may be a uniform structure in which the polymer composition in the particles is uniform, or a core / shell structure in which the central portion and the outer peripheral portion have different polymer compositions. .

The average particle size of the component (A) is not particularly limited, but it is preferably in the range of 10 to 10,000 nm from the following points. When the average particle diameter is 10 nm or more, the dispersibility when blending the sizing agent tends to be better, and
When it is 0 nm or less, a uniform film tends to be formed on the glass fiber surface. Further, the average particle size is more preferably 5000 nm or less, and particularly preferably 1000 nm or less, from the viewpoint that a more uniform film is formed on the glass fiber surface. Further, the average particle size is more preferably 50 nm or more, and particularly preferably 100 nm or more, from the viewpoint that the dispersibility at the time of blending the sizing agent is further improved.

The weight average molecular weight of the component (A) is not particularly limited, but when the component (A) is a non-crosslinked polymer, it is preferably in the range of 1,000 to 300,000 from the following points. When the weight average molecular weight is 1000 or more, the mechanical properties of the resin molded product tend to be better, and when it is 300,000 or less, the openability of the glass fiber bundle is further improved, and the glass fiber traces on the surface of the resin molded product are raised. And the appearance tends to be better. Furthermore, from the point that the appearance becomes even better,
The weight average molecular weight of the component (A) is more preferably 100,000 or less, particularly preferably 50,000 or less. In addition, since the mechanical properties are further improved, the weight average molecular weight of the component (A) is 2
000 or more is more preferable, and 5000 or more is particularly preferable. When the component (A) has a core / shell structure,
The weight average molecular weight of the polymer constituting the core portion and the shell portion is not particularly limited, but the weight average molecular weight of the polymer constituting the shell portion is preferably in the same range as the above range.

The glass transition temperature of the component (A) is not particularly limited, but it is preferably in the range of -20 to 80 ° C from the following points. When the glass transition temperature is -20 ° C or higher, the stickiness of the film tends to be lower or eliminated, and when the glass transition temperature is 80 ° C or lower, the film formation tends to be better. Further, the glass transition temperature of the component (A) is more preferably 60 ° C. or lower from the viewpoint that the film formation is performed more favorably, and 0 ° C. or higher from the viewpoint that stickiness is further reduced. When the component (A) has a core / shell structure, the glass transition temperature of the polymer constituting the core portion and the shell portion is not particularly limited, but from the viewpoint of stickiness and film formation, the glass of the shell portion is formed. The transition temperature is preferably in the same range as the above range.

The component (A) has a (meth) acrylic monomer unit as its constituent component, and a monomer forming the (meth) acrylic monomer unit (used for polymerization (meth)). As the acrylic monomer), a monomer having a (meth) acryloyl group (methacryloyl group or acryloyl group, or methacryloyl group and acryloyl group) can be used, and is not particularly limited.

For example, an alkyl group having 1 to 20 carbon atoms such as methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate and t-butyl (meth) acrylate. (Meth) acrylate having an ester group having an aromatic ring such as benzyl (meth) acrylate; (meth) acrylate having an ester group having a cyclohexane ring such as cyclohexyl (meth) acrylate; isobornyl (Meth) acrylate having an ester group having a bicyclo ring such as (meth) acrylate; tricyclo [5.2.1.0 ^2,6 ].
(Meth) acrylate having an ester group having a tricyclo ring such as decanyl (meth) acrylate; 2,2,2
-(Meth) acrylate having an ester group having a fluorine atom such as trifluoroethyl (meth) acrylate,
Hydrophobic (meth) acrylic monofunctional monomer such as (meth) acrylonitrile; hydroxyalkyl (meth) acrylate having a hydroxyalkyl group such as hydroxyethyl (meth) acrylate; polyethylene glycol (meth) acrylate, polypropylene glycol ( (Meth) acrylate having an ester group having a polyalkylene glycol chain such as (meth) acrylate; (meth) acrylate having an ester group having a cyclic ether structure such as glycidyl methacrylate and tetrahydrofurfuryl (meth) acrylate; (meth) acrylamide Hydrophilic nonionic (meth) acrylic monofunctional monomers such as; 2- (meth) acryloyloxyethyl succinic acid,
2- (meth) acryloyloxyethyl phthalic acid, 2-
(Meth) acrylate having a carboxyl group such as (meth) acryloyloxyethylhexahydrophthalic acid;
(Meth) acrylic acid; hydrophilic anionic (meth) acrylic monofunctional monomer such as (meth) acrylic acid metal salt; ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di ( (Meth) acrylate, polypropylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4-butylene glycol di (meth) acrylate, polybutylene glycol di (meth) acrylate, neopentyl glycol di ( (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth)
Acrylate, 1,10-decanediol di (meth) acrylate, dimethylolethanedi (meth) acrylate, 1,1-dimethylolpropane di (meth) acrylate, 2,2-dimethylolpropane di (meth) acrylate, tri Methylolethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylolmethane tri (meth) acrylate, tetramethylolmethane di (meth) acrylate,
Examples thereof include a polyvalent ester of (meth) acrylic acid and a polyhydric alcohol [for example, pentaerythritol, dipentaerythritol, etc.], and a (meth) acrylic polyfunctional monomer such as allyl (meth) acrylate.

These monomers may be used alone or in combination of two or more as required. Among them, alkyl (meth) acrylate, having an aromatic ring (meth)
Acrylate, (meth) acrylate having a cyclohexane ring, (meth) acrylate having a bicyclo ring,
Hydrophobic (meth) acrylic monofunctional monomers such as (meth) acrylate having a tricyclo ring and (meth) acrylate having a fluorine atom, and a hydroxyalkyl (meth) acrylate and a polyalkylene glycol chain (meth) Hydrophilic (meth) acrylic monofunctional monomers such as acrylates, (meth) acrylates having a cyclic ether structure, (meth) acrylates having a carboxyl group, (meth) acrylic acid, and (meth) acrylates having an amino group. Is preferably used in combination. Obtained by polymerizing hydrophobic (meth) acrylic monomers (meth)
In the case of an acrylic polymer, the water resistance and weather resistance of a resin molded product obtained by using a glass fiber sizing agent containing the same tend to be improved. Further, in the case of a (meth) acrylic polymer obtained by polymerizing a hydrophilic (meth) acrylic monomer, the stability of the glass fiber sizing agent containing the same tends to be improved, and at the same time, the glass fiber and the sizing agent The adhesiveness with the agent component becomes good, and as a result, the converging property of the glass fiber bundle and the cutting processability of the glass fiber bundle tend to be improved. Therefore, by using both, it is possible to achieve both advantages. Among the hydrophobic (meth) acrylic monofunctional monomers, alkyl (meth) acrylate is more preferable, and among the hydrophilic (meth) acrylic monofunctional monomers, hydroxyalkyl (meth) acrylate, Nonionic (meth) acrylic monofunctional monomers such as polyalkylene glycol (meth) acrylate and (meth) acrylate having a cyclic ether structure are more preferable.

The combination method is not particularly limited, and the hydrophobic (meth) acrylic monofunctional monomer and the hydrophilic (meth) acrylic monofunctional monomer are separately polymerized and then mixed. Alternatively, the hydrophobic (meth) acrylic monofunctional monomer and the hydrophilic (meth) acrylic monofunctional monomer may be copolymerized. Among them, the combined use by copolymerization is preferable.

Further, the component (A) has, as its constituent components, a (meth) acrylic compound in addition to the (meth) acrylic monomer unit.
It may have a unit of another monomer copolymerizable with the acrylic monomer. Such other monomers include styrene, aromatic vinyl such as divinylbenzene, vinyl acetate, vinyl chloride, maleic anhydride, maleic acid,
Examples include monomers such as maleic acid ester, fumaric acid, fumaric acid ester, and triaryl isocyanurate.
In this case, the (meth) acrylic monomer is the main component, that is, among the monomer units constituting the copolymer,
The content of the (meth) acrylic monomer unit is preferably 50 mol% or more in the copolymer component. The lower limit of this content is more preferably 60 mol% or more,
It is more preferably 70 mol% or more, and particularly preferably 80 mol% or more. Moreover, the upper limit of this content is not particularly limited.

The polymerization method for preparing the component (A) is
There is no particular limitation, and known polymerization methods such as bulk polymerization, suspension polymerization, emulsion polymerization, solution polymerization and the like can be used. Of these, an emulsion polymerization method is preferred, in which the polymer is obtained in the form of an emulsion. Even by a polymerization method other than emulsion polymerization, an emulsion can be made by emulsifying the polymer once polymerized by a known method.

Component (B) is a water-soluble polymer containing a (meth) acrylamide unit as at least one polymerizing component, and is a homopolymer of (meth) acrylamide, copolymerizable with (meth) acrylamide and (meth) acrylamide. Copolymers with other monomers can be used. In addition,
Here, "water-soluble" means 1 g in 1000 g of water at 20 ° C.
It means the property of completely dissolving the polymer when the polymer is added and stirred.

The component (B) can assist in improving the compounding stability of the sizing agent, improving the sizing property of the glass fiber, and forming a film.

The component (B) is not particularly limited as long as it is water-soluble, but it is preferable that it has no cloud point in the range of 20 to 90 ° C. This is because the stability of the emulsion tends to improve when the cloud point is not within this range.

The content of the (meth) acrylamide unit in the constituent component of the component (B) is not particularly limited, but among the monomer units constituting the component (B), the (meth) acrylamide monomer unit is It is preferably 1 mol% or more. The content of the (meth) acrylamide monomer unit is more preferably 10 mol% or more, and particularly preferably 30 mol% or more, from the viewpoint of more sufficiently obtaining desired characteristics.

The weight average molecular weight of the component (B) is not particularly limited, but is preferably in the range of 10,000 to 1,000,000 from the following points. When the weight average molecular weight is 10,000 or more, the stability of the glass fiber sizing agent at the time of compounding and preparation tends to be improved, and when it is 1,000,000 or less, the stability of the emulsion tends to be improved. Furthermore, the weight average molecular weight is 5 from the viewpoint of stability when adjusting the composition.
It is more preferably 10,000 or more, particularly preferably 100,000 or more. From the viewpoint of emulsion stability, the weight average molecular weight is 5
It is more preferably 0,000 or less, particularly preferably 300,000 or less.

The monomer unit which is a component other than the (meth) acrylamide unit which is an essential component constituting the component (B) is not particularly limited, but a monomer unit which forms a monomer unit of the other component. Examples of the body include N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N.
-Diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, acryloylmorpholine,
Monomers having a (meth) acrylamide skeleton such as (meth) acrylamide ethyl ethylene urea; hydroxyethyl (meth) acrylate, hydroxypropyl (meth)
Hydroxyalkyl (meth) acrylates such as acrylates; (meth) acrylates of polyethylene glycol having 2 to 40 repeating units; (meth) acrylic acid; dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, methacryloyloxyethyl (Meth) acrylate having an amino group such as trimethylammonium chloride; alkyl (meth) acrylate exemplified as a monomer usable for the production of the component (A), (meth) acrylate having an ester group having an aromatic ring, (Meth) acrylate having ester group having cyclohexane ring, (meth) acrylate having ester group having bicyclo ring, (meth) acrylate having ester group having fluorine atom, ester having cyclic ether structure The a (meth) acrylate,
Examples thereof include polyhydric esters of (meth) acrylic acid and polyhydric alcohol, and (meth) acrylic polyfunctional monomers.

Among them, N, N-dimethyl (meth) acrylamide, N-isopropylacrylamide, acryloylmorpholine, hydroxyethyl (meth) acrylate, polyethylene glycol (meth) acrylate,
Monomers whose homopolymer is water-soluble, such as (meth) acrylic acid, dimethylaminoethyl (meth) acrylate, and methacryloyloxyethyltrimethylammonium chloride, are preferred. Furthermore, nonionic water-soluble monomers such as hydroxyethyl methacrylate and polyethylene glycol methacrylate are more preferable. This is because when a nonionic water-soluble monomer is used, the stability of the glass fiber sizing agent at the time of blending and preparation tends to be improved.

These monomers can be used alone or in a combination of two or more kinds with (meth) acrylamide which is an essential component, if necessary. In that case, the (meth) acrylamide unit in the component of the component (B),
The total number of the water-soluble monomer units of the homopolymer is 5
It is preferably 0 mol% or more. When this total is 50 mol% or more, the stability of the emulsion tends to be improved. From the point of obtaining a more sufficient effect, this total value is 7
0 mol% or more is more preferable, and 90 mol% or more is particularly preferable.

The polymerization method for preparing the component (B) is as follows:
There is no particular limitation, and known polymerization methods such as bulk polymerization, suspension polymerization, emulsion polymerization, solution polymerization and the like can be used. Among them, the solution polymerization method is preferable, and the aqueous solution polymerization method is more preferable.

The content ratio of the component (A) and the component (B) is not particularly limited, but from the following points, the content of the component (B) is 0.1 to 100 relative to 100 parts by mass of the component (A). A range of parts by mass is preferred. When the content of the component (B) is 0.1 part by mass or more, the stability during compounding and preparation of the sizing agent tends to be good, and when it is 100 parts by mass or less, the water resistance of the resin molded product tends to be good. . Further, from the viewpoint of stability during preparation of the sizing agent, the content of the component (B) is more preferably 50 parts by mass or less, and particularly preferably 10 parts by mass or less, relative to 100 parts by mass of the component (A). From the viewpoint of water resistance of the molded product, the content of the component (B) is more preferably 0.5 part by mass or more, and particularly preferably 1 part by mass or more, relative to 100 parts by mass of the component (A).

The total content (mass ratio) of the component (A) and the component (B) with respect to the entire glass fiber sizing agent emulsion of the present invention is not particularly limited, but from the viewpoint of sufficiently obtaining the desired effect. The range of 10 to 60 mass% is preferable, and in this range, 50 mass% or less is more preferable.
Moreover, 30 mass% or less is more preferable.

The glass fiber sizing agent emulsion of the present invention can take a form in which the component (A) is dispersed in water as a dispersion medium and the component (B) is dissolved.

The method for producing the emulsion for a glass fiber sizing agent of the present invention is not particularly limited. For example, the component (A) and the component (B) may be separately polymerized and then blended, or the component (A) may be emulsion polymerized to form an emulsion, and then the component (A) may be added in the presence of the component (A). The component (B) may be polymerized in an aqueous solution, or the component (B) may be polymerized in an aqueous solution first, and then the component (A) may be emulsion polymerized in the presence of the component (B) to give an emulsion. Of these, preferred are those obtained by first polymerizing the component (B) in an aqueous solution and then emulsion-polymerizing the component (A) in the presence of the component (B).

The glass fiber sizing agent emulsion of the present invention contains, in addition to the components (A) and (B), an emulsifier, polymer particles other than (meth) acrylic, and (meth) acrylamide units, if necessary. You may contain the water-soluble polymer etc. which are not included as a polymerization component.

The emulsifier can improve the stability at the time of polymerizing the emulsion for glass fiber sizing agent or at the time of preparing the glass fiber sizing agent. The type of emulsifier is not particularly limited, and examples thereof include a cationic emulsifier, an anionic emulsifier, an amphoteric emulsifier, a nonionic emulsifier, and a reactive emulsifier. These may be used alone or as needed 2
One or more species can be used in combination.

Specific examples of the cationic emulsifier include quaternary ammonium salts such as lauryltrimethylammonium chloride, cetyltrimethylammonium chloride and stearyltrimethylammonium chloride, amine salts such as stearylamine acetate, stearylamine hydrochloride and stearylamine oleate. Is mentioned.

Specific examples of anionic emulsifiers include fatty acid salts such as sodium stearate and potassium oleate, sodium lauryl sulfate, ammonium lauryl sulfate, alkyl sulfate ester salts such as sodium polyoxyethylene lauryl ether sulfate, and sodium dodecylbenzenesulfonate. , Sodium dioctyl sulfosuccinate, sodium alkyldiphenyl ether disulfonate, and the like sulfonates.

Specific examples of the amphoteric emulsifier include alkyl betaines such as lauryl betaine and stearyl betaine.

Specific examples of the nonionic emulsifier include polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether and other polyoxyethylene alkyl ethers, polyoxyethylene octylphenyl ether, Polyoxyethylene alkyl allyl ethers such as polyoxyethylene nonyl phenyl ether, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate and other polyoxyethylene sorbitan fatty acid esters, polyethylene glycol stearate and other polyoxyethylene fatty acid esters Is mentioned.

Specific examples of commercially available reactive emulsifiers include:
Latemur S-120A, S-180A manufactured by Kao Corporation,
Asahi Denka Kogyo Co., Ltd. ADEKA rear soap SE-5N, S
E-10N, SE-20N, NE-10, NE-20,
NE-30, NE-40, NE-50, NE-80, N
E-100, Antox-MS- manufactured by Nippon Emulsifier Co., Ltd.
60, Antox-MS-20, Antox-MS-2
N, Antox-MS-NH4, RA-1020, RA
-1120, RA-1820, RF-751, RMA-
564, RMA-568, RMA-506, RMA-1
120, RMA-1020, RMA-2320 (all are trade names) and the like.

The addition amount of the emulsifier is not particularly limited as long as the desired characteristics are obtained, but from the viewpoint of water resistance and weather resistance of the resin molded product, it is 10% by mass with respect to the mass of the component (A). The following range is preferable, 7 mass% or less is more preferable, and 5 mass% or less is particularly preferable.

Next, the glass fiber sizing agent of the present invention will be described.

The glass fiber sizing agent in the present invention contains the emulsion for glass fiber sizing agent of the present invention as an essential component, but if necessary, other components such as a surface treatment agent, a lubricant and an antistatic agent may be added. It may be contained.

The surface treatment agent is a component having a role of chemically bonding the glass fiber and the matrix resin.
Known coupling agents such as acrylic silane, vinyl silane, mercapto silane, amino silane and glycidyl silane are used. For a silane coupling agent such as (meth) acrylic silane or vinyl silane which is hardly soluble in water as it is, it is preferable to add an acid such as acetic acid to solubilize it in water before use.

The lubricant is a component that imparts appropriate slipperiness to the glass fiber bundle, reduces friction when passing through the process, and protects the fibers. Types of lubricants include plant waxes such as candelilla wax, carnauba wax, and wood wax; animal waxes such as beeswax, lanolin, and whale wax;
Mineral wax such as montan wax, ceresin and petroleum wax; synthetic wax such as polyalkylene such as polyethylene, polyethylene glycol, polyethylene ester, chloronaphthalene, sorbital and polychloropolyfluoroethylene; fatty acid such as palmitic acid amide and stearic acid amide Amides such as amides, stearic acid condensates of tetraethylene pentamine, and pelargonic acid condensates of triethylene tetramine, and their salts; alkyl imidazoline derivatives; higher alcohols such as lauryl alcohol and stearyl alcohol; saturated fatty acids, unsaturated fatty acids, saturated fatty acids Known materials such as ester-based, fatty acid ether-based, aromatic ester-based, aromatic ether-based surfactants and modified silicone oils are used.

The antistatic agent is a component for removing static electricity generated when the glass fiber bundle passes through the process, and includes inorganic salts such as lithium chloride and aluminum chloride, carboxylates,
Known materials such as quaternary ammonium salts such as sulfonic acid salts, sulfuric acid ester salts, phosphoric acid ester salts, lauryl trimethyl ammonium chloride, cetyl trimethyl ammonium chloride, and stearyl trimethyl ammonium chloride are used.

The compounding amount of the emulsion for glass fiber sizing agent, which is an essential component, is not particularly limited, but from the viewpoint of obtaining desired properties, the amount of the component (A) and the component (B) relative to the whole glass fiber sizing agent is increased. The ratio of the total amount is 1 to 30% by mass
It is preferable to mix them in such a range. Above all 5
The range of up to 20% by mass is more preferable.

The glass fiber sizing agent is prepared by adding the emulsion for a glass fiber sizing agent of the present invention, and optionally other components, stirring and mixing, and adding water as necessary to adjust the concentration of a predetermined solid content. It can be manufactured.

Next, the glass fiber bundle of the present invention will be described.

The glass fiber bundle in the present invention is obtained by treating the glass fibers with the glass fiber sizing agent of the present invention and bundling them, and the glass fibers are bound in a unit of, for example, 50 to 4000.

The amount of the glass fiber sizing agent applied to the glass fiber bundle is not particularly limited, but the solid content of the glass fiber sizing agent is preferably in the range of 0.1 to 2% with respect to the mass of the glass fibers. .

The diameter of the glass fiber is not particularly limited, but is preferably in the range of 3 to 20 μm, more preferably 5 to 15 μm.

The length of the glass fiber bundle is not particularly limited.
It may be continuous roving or chopped strands cut to a specific length.

The glass fiber bundle of the present invention is produced, for example, by coating the glass fiber with a glass fiber sizing agent using a roller coater, winding the resulting glass fiber strand, and then drying it under predetermined drying conditions. can do.

Next, the resin composition of the present invention will be described.

The resin composition of the present invention comprises the glass fiber bundle of the present invention.

The form of the glass fiber bundle in the resin composition of the present invention is not particularly limited. The shape of the used fiber bundle may be maintained, the fiber may be partially opened, or the fiber may be completely opened and each glass fiber may be independent.

The content of the glass fiber bundle is not particularly limited, but is preferably in the range of 0.1 to 80 mass% in the resin composition from the following points. When the content of the glass fiber bundle is 0.1% by mass or more, the mechanical strength of the resin molded product tends to be good,
When the content is 80% by mass or less, the protrusion of fiber marks on the surface of the resin molded product is reduced, and the appearance of the resin molded product tends to be good. Further, the content of the glass fiber bundle is more preferably 60% by mass or less, from the viewpoint of the appearance of the resin molded product,
The following are particularly preferred. The content of the glass fiber bundle is
From the viewpoint of mechanical strength of the resin molded product, 1% by mass or more is more preferable, and 20% by mass or more is particularly preferable.

The length of the glass fiber bundle is not particularly limited, but is preferably in the range of 0.5 mm or more. When the length of the glass fiber bundle is 0.5 mm or more, the strength of the resin molded product tends to be more sufficiently improved. From this point, 1 mm or more is more preferable, and 10 mm or more is particularly preferable. There is no upper limit on the length, which is appropriately set according to the desired characteristics and processability, and may be continuous in the resin composition.

The resin (matrix resin) used in the resin composition of the present invention is not particularly limited, and examples thereof include (meth) acrylic resin, unsaturated polyester resin, epoxy resin, phenol resin, polypropylene, polyethylene terephthalate and polyamide. It can be used for polycarbonate, etc. Above all, it is preferable to use a (meth) acrylic resin as a main component from the viewpoint of weather resistance.

The content of the resin in the resin composition is not particularly limited, but is preferably in the range of 1 to 99.9 mass% in the resin composition from the following points. When the content of the resin is 1% by mass or more, the appearance of the resin molded product tends to be good, and 99.9%
Below, the mechanical strength of the resin molded product tends to be good. Further, the content of the resin is more preferably 50% by mass or less, and particularly preferably 20% by mass or less, from the viewpoint of mechanical strength of the resin molded product. Further, the content of the resin is more preferably 3% by mass or more, and particularly preferably 5% by mass or more from the viewpoint of the appearance of the resin molded product.

The resin composition of the present invention contains, in addition to the glass fiber bundle and the resin, optionally a polymerizable monomer, an inorganic filler,
Polymerization initiators, polymerization inhibitors, pigments, thickeners, internal release agents, etc. can also be used.

The type of polymerizable monomer is not particularly limited, but it is preferable to use a (meth) acrylic monomer from the viewpoint of weather resistance. Above all, it is preferable to use the (meth) acrylic monomers listed as the monomer forming the constituent component of the component (A).

The content of the polymerizable monomer is not particularly limited, but is preferably 3 to 98% by mass in the resin composition from the following points. When the content of the polymerizable monomer is 3% or more, the fluidity of the resin composition tends to be improved, and when the content is 98% by mass or less, the polymerization shrinkage of the resin molded product is small, and the dimensional stability of the resin molded product is reduced. The tendency is to improve. Further, the content of the polymerizable monomer is 6 from the viewpoint of polymerization shrinkage of the resin molded product.
0 mass% or less is more preferable, and 30 mass% or less is particularly preferable. In addition, the content of the polymerizable monomer is more preferably 5% by mass or more, and particularly preferably 10% by mass or more, from the viewpoint of fluidity of the resin composition. The polymerizable monomer can form a matrix resin by polymerization.

The kind of the inorganic filler is not particularly limited, and examples thereof include calcium carbonate, magnesium carbonate, aluminum hydroxide, magnesium hydroxide, calcium hydroxide, silica, fused silica, barium sulfate, titanium oxide, magnesium oxide, and oxide. Known materials such as calcium, aluminum oxide, calcium phosphate, talc, mica, clay and glass powder can be used, and two or more kinds of them can be used in combination.

The content of the inorganic filler is not particularly limited, but is preferably 80% by mass or less in the resin composition from the following points. When the content of the inorganic filler is 80% by mass or less, the gloss of the resin molded product surface is improved, and the appearance of the resin molded product tends to be good. From this point, 60% by mass or less is more preferable, and 50% by mass or less. Is particularly preferable. Further, the content of the inorganic filler is 5 because the effect of its addition is sufficiently exhibited.
Mass% or more is preferable, and 20 mass% or more is more preferable.

The type of polymerization initiator is not particularly limited. For example, known materials such as organic peroxides such as t-butylperoxybenzoate and t-amylperoxybenzoate and azo compounds such as azobisisobutyronitrile can be used.

The type of thickener is not particularly limited. Known materials such as polymer powder and metal oxides such as magnesium oxide can be used.

The internal release agent is not particularly limited. For example, known materials such as a fatty acid metal salt such as zinc stearate and a surfactant such as sodium dialkylsulfosuccinate can be used.

The form of the resin composition is not particularly limited. For example, Sheet Molding Compound, which is a sheet-shaped molding mixture,
It may be a semi-solid material such as bulk molding compound which is a lump-like molding mixture, a solid material such as pellets, a liquid material such as slurry and syrup. Above all, in view of heat resistance, chemical resistance and productivity of the resin molded product, it is preferable to take a form of a semi-solid material such as a sheet molding compound or a bulk molding compound. Further, a sheet molding compound is more preferable from the viewpoint of strength of the resin molded product.

The method for producing the resin composition of the present invention is not particularly limited. For example, when the resin composition is a liquid such as syrup or slurry, the resin, the glass fiber bundle, and optionally other additives may be mixed using a known mixer for low viscosity such as a mixer. Further, when the resin composition is a semi-solid material such as a bulk molding compound, a resin, a glass fiber bundle, and optionally other additives, for high viscosity such as a kneader, a continuous kneader, an extruder. The kneading may be performed using a known mixing device. When the resin composition is a sheet molding compound, the glass fiber bundle is impregnated with the resin and, if necessary, other additives using a known device such as an SMC machine as shown in FIG. It can be manufactured by increasing the viscosity. When the resin composition is a solid material such as pellets, the resin, the glass fiber bundle and, if necessary, other additives may be melt-kneaded using a known device such as an extruder.

Next, the resin molded product of the present invention will be described.

The resin molded product of the present invention comprises the glass fiber bundle of the present invention.

The form of the glass fiber bundle in the resin molded product of the present invention is not particularly limited. The shape of the used fiber bundle may be maintained, the fiber may be partially opened, or the fiber may be completely opened and each glass fiber may be independent.

The content of the glass fiber bundle is not particularly limited, but is preferably in the range of 0.1 to 80 mass% in the resin molded product from the following points. When the content of the glass fiber bundle is 0.1% by mass or more, the mechanical strength of the resin molded product tends to be good,
If it is 80% by mass or less, the appearance of the resin molded product tends to be good. Further, the content of the glass fiber bundle is more preferably 60% by mass or less, and particularly preferably 50% by mass or less, from the viewpoint of the appearance of the resin molded product. Further, the content of the glass fiber bundle is more preferably 1% by mass or more, and particularly preferably 20% by mass or more, from the viewpoint of mechanical strength of the resin molded product.

The length of the glass fiber bundle is not particularly limited, but is preferably 0.5 mm or more. When the length of the glass fiber bundle is 0.5 mm or more, the strength of the resin molded product tends to be more sufficiently improved. From this point, 1 mm or more is more preferable, and 10 mm or more is particularly preferable. There is no upper limit of the length, which is appropriately set according to the desired characteristics, and may be continuous in the resin molded product.

The resin (matrix resin) used in the resin molded product of the present invention is not particularly limited, and examples thereof include (meth) acrylic resin, unsaturated polyester resin, epoxy resin, phenol resin, polypropylene, polyethylene terephthalate and polyamide. , Polycarbonate, etc. can be used. Above all, it is preferable to use a (meth) acrylic resin from the viewpoint of weather resistance.

The content of the resin in the resin molded product is not particularly limited, but is preferably in the range of 1 to 99.9 mass% in the resin molded product from the following points. When the content of the resin is 1% by mass or more, the appearance of the resin molded product tends to be good, and when it is 99.9% by mass or less, the mechanical strength of the resin molded product tends to be good.

In addition to the glass fiber bundle and the resin, if necessary, an inorganic filler, a pigment or the like can be used.

The inorganic filler is not particularly limited, and the same inorganic filler as that used in the resin composition can be used.

The content of the inorganic filler is not particularly limited, but is preferably in the range of 80% by mass or less in the resin molded product from the following points. When the content of the inorganic filler is 80% by mass or less, the resin molded article tends to have a good appearance.
It is more preferably not more than mass%, particularly preferably not more than 50 mass%. Further, the content of the inorganic filler is preferably 5% by mass or more, and more preferably 20% by mass or more, from the viewpoint that the effect of adding the inorganic filler is sufficiently exhibited.

The method for producing the resin molded product is not particularly limited. For example, by molding the resin composition of the present invention using a known molding method such as a compression molding method, an injection molding method, a mold molding method, a hand layup method, a resin transfer method, a spray up method, or a pultrusion molding method. The resin molded product of the present invention can be manufactured. Of these, the compression molding method is preferable.

[0103]

EXAMPLES The present invention will be specifically described below with reference to examples. All "parts" and "%" in the examples are based on mass.

[Weight Average Molecular Weight of Component (A)] The polystyrene reduced value was determined by the GPC method under the following conditions.

Filtration conditions: 0.5 μm Teflon (registered trademark) membrane filter for filtering sample solution: Tosoh Corp., high-speed GPC device HLC-812
0 column: TSKgel G2000HXL and TS manufactured by Tosoh Corporation
Two KgelG4000HXL connected in series (when the weight average molecular weight is 100,000 or less), three Tosoh Co., Ltd., TSKgelGMMHXL connected in series (when the weight average molecular weight exceeds 100,000 and less than 1,000,000) Oven temperature : 40 ° C Eluent: Tetrahydrofuran Sample concentration: 0.4% (when weight average molecular weight is 100,000 or less), 0.38% (when weight average molecular weight exceeds 100,000 and less than 1,000,000) Flow rate: 1 ml / Injection amount: 0.1 ml Detector: RI (differential refractometer).

[Weight Average Molecular Weight of Component (B)] A polyethylene glycol conversion value was determined by the GPC method under the following conditions.

Filtration conditions: 0.5 μm Teflon membrane filter for filtering sample solution: Tosoh Corp., high-speed GPC device HLC-802
0 column: Tosoh Corp., TSK-gel α-M 3
Connected in series in series Oven temperature: 40 ° C. Eluent: 50 mM aqueous solution of phosphoric acid Sample concentration: 0.2% Flow rate: 1 ml / min Injection amount: 0.1 ml Detector: RI (differential refractometer).

[Average Particle Size] The volume average particle size was measured using a laser diffraction / scattering type particle size distribution measuring device (LA-910, manufactured by Horiba Ltd.).

[Glass Transition Temperature (Tg)] In the case where the polymer of the component (a) is a copolymer obtained by polymerizing n kinds of monomers, n kinds of monomers forming the copolymer are selected. From the glass transition temperature (° C.) of the homopolymer of the monomer, Tg was calculated using the following formula (1), and fractions below the decimal point were rounded off. Further, the glass transition temperature of a homopolymer is described in “Polymer Data Handbook” edited by The Polymer Society of Japan (Baifukan, 1986).
Issued in January of the year) was used.

[0110]

[Equation 1] Tg: glass transition temperature (° C.) of copolymer Tg _(i) : glass transition temperature (° C.) of homopolymer of i component w _i : mass ratio of i component, Σw _i = 1

[Evaluation of compounding stability of glass fiber sizing agent] ⊚: No agglomerates generated during compounding preparation, no change after standing for 1 week, ○: No agglomerates generated during compounding preparation, even after standing for 3 days No change, Δ: No agglomerate generation during formulation preparation, precipitate generation after standing for 3 days, ×: Agglomerate generation during formulation preparation.

[Evaluation of Cutting Processability of Glass Fiber Bundle] ○: The cutting processability of the glass fiber bundle is good, and the glass fiber bundle can be easily cut by the cutter of the SMC machine. Δ: Cutting process of the glass fiber bundle The property is poor, and the glass fiber bundle cannot be cut with the cutter of the SMC machine.

[Evaluation of Appearance of Resin Molded Product] O: No embossment of glass fiber or the like is observed on the surface of the molded product, X: Embossment of glass fiber or the like is observed on the surface of the molded product.

[Weather resistance test of resin molded product (accelerated exposure test)] Sunshine Super Long Life Weatherometer WEL-SUN-HC-B type manufactured by Suga Test Instruments Co., Ltd., black panel temperature 63 ° C., 60 minutes The molded product was subjected to a 500-hour accelerated exposure test under the condition of rainfall (spray) for 12 minutes, and the appearance after the test was visually confirmed.

◯: No occurrence of cracks or deterioration of resin is observed, Δ: Some occurrence of cracks along the glass fiber is observed.

X: Cracks are observed along the glass fiber.

[Production Example of Acrylic Syrup (SR1)] Pure water 435 parts, polyvinyl alcohol (saponification degree 88%, degree of polymerization 1000) 1 in a reaction vessel equipped with a cooling pipe, a thermometer, a stirrer, and a nitrogen introducing pipe. After dissolving 15 parts, 289.5 parts of methyl methacrylate, 10.5 of methacrylic acid
Part, 9 parts of octyl thioglycolate, 0.6 parts of azobisisobutyronitrile were dissolved in the monomer solution,
7 hours in 1 hour while stirring at 350 rpm under nitrogen atmosphere
The temperature was raised to 0 ° C. and the heating was continued for 2 hours. Then 90
The temperature was raised to ℃ and heated for 2 hours to complete the suspension polymerization. The obtained slurry was filtered, washed, and then dried with a hot air dryer at 50 ° C. to obtain an acrylic polymer having an average particle diameter of 350 μm. The weight average molecular weight of the obtained acrylic polymer was 35,000.

Next, in a reaction vessel equipped with a cooling tube, a thermometer and a stirrer, 56.7 parts of methyl methacrylate and 11.1 parts of neopentyl glycol dimethacrylate and 2,6-di-t- as a polymerization inhibitor were added. Butyl-4-methylphenol (Sumitomo Chemical Co., Ltd., trade name, "Sumilyzer B"
HT ") 0.014 parts and the above-mentioned acrylic polymer particles 32.2 parts were charged and the acrylic polymer was dissolved at 60 ° C for 3 hours to obtain an acrylic syrup (SR1).

[Example 1] 150 pure water was placed in a reaction vessel equipped with a cooling pipe, a thermometer, a stirrer, a dropping device and a nitrogen introducing pipe.
And 5 parts of acrylamide were charged and the temperature was raised to 80 ° C. with stirring under a nitrogen atmosphere. After confirming that the internal temperature reached 80 ° C, potassium persulfate 0.3 was added as a polymerization initiator.
Part of the mixture, and the mixture was polymerized for 15 minutes to prepare an aqueous solution of polyacrylamide (component (B)). Subsequently, 70 parts of methyl methacrylate and 24 parts of n-butyl acrylate
Part, 6 parts of glycidyl methacrylate, 1 part of octyl mercaptan as a chain transfer agent, and 1 part of sodium dialkylsulfosuccinate (trade name "Perex OT-P" manufactured by Kao Corporation) as a surfactant over 4 hours. The mixture is dropped into a reaction vessel, emulsion polymerization is carried out in the presence of the component (B), the temperature is kept at 80 ° C. for 1 hour and then cooled to room temperature to end the emulsion polymerization, and the component (A) (methyl methacrylate / n -Butyl acrylate / glycidyl methacrylate copolymer) and an emulsion containing component (B) (polyacrylamide) was obtained. The average particle diameter of this emulsion is 420 nm, the weight average molecular weight of component (A) in this emulsion is 25,000, the glass transition temperature is 50 ° C., and the weight average molecular weight of component (B) is 1400.
It was 00.

Next, this emulsion was diluted with pure water to a solid content of 8
% Of γ-methacryloxypropyltrimethoxysilane and 0.2 part of a stearic acid condensate of tetraethylenepentamine, which had been made soluble in acetic acid, were added and stirred to prepare a glass fiber sizing agent. . No agglomerates were generated in this step, and the composition was stable. Again 7
It was stable even after being left for a day, and neither aggregates nor precipitates were found.

Next, the glass fiber sizing agent of the present invention was applied to the glass fibers and bundled in units of 200 glass fibers to give 1
It heat-processed at 40 degreeC for 12 hours, and it was set as the glass fiber bundle. The present glass fiber bundle was in a well-focused state, and the cutability of the fiber bundle was also good.

Next, a sheet molding compound was manufactured using the SMC machine shown in FIG. 1 in the following procedure.

The following compound (resin composition) 1 was applied onto the film 2, and the glass fiber bundle 4 was cut to a length of 25 mm by the cutter 5 and spread on the applied surface, and then the same compound 2 was applied. I covered the top with and closed it. Then, the whole was passed through a pressure roller (rolling roller) 6 to impregnate the glass fiber with the same compound, and subsequently formed into a sheet, which was wound around a winding roller 7 and aged at 40 ° C. for 4 days to obtain a sheet molding compound.

Composition of compound: 31.5 parts of acrylic syrup (SR1), calcium carbonate (manufactured by Nitto Dokuka Kogyo Co., Ltd., trade name "NS")
# 200 ") 38.5 parts, zinc stearate 0.1 part, polymerization initiator (manufactured by Kayaku Akzo Co., Ltd., trade name" Trigonox 42 ") 0.7 part, pigment 2.3 parts, magnesium oxide ( Kyowa Chemical Industry Co., Ltd., trade name "Magmic") 0.08 parts, glass fiber bundle 30 parts.

The sheet molding compound thus obtained was cut into a size of 140 mm × 140 mm, and 125
Press molding was carried out for 4 minutes at a pressure of 15 MPa in a mold heated at 0 ° C. to obtain a resin molded product of 200 mm × 200 mm × 4 mm. The appearance of the molded product was good.

The obtained molded product is 50 mm × 70 mm × 4
It was cut into a size of mm and the above-mentioned weather resistance test was performed.
After the test, no cracking or resin deterioration was observed on the surface of the molded product, and the weather resistance was good.

[Example 2] In the production process of the component (B), 2.5 parts of acrylamide and 2.5 parts of hydroxyethyl methacrylate were used instead of 5 parts of acrylamide.
An emulsion for glass fiber sizing agents was obtained in the same manner as in Example 1 except that parts were used.

A glass fiber sizing agent was obtained in the same manner as in Example 1 except that this glass fiber sizing agent emulsion was used. No agglomerates were generated in this step, and the composition was stable. Further, it was stable even after standing for 7 days, and neither aggregates nor precipitates were observed.

A glass fiber bundle was obtained in the same manner as in Example 1 except that this glass fiber sizing agent was used. The present glass fiber bundle was in a well-focused state, and the cutability of the fiber bundle was also good.

Example 1 except that this glass fiber bundle was used
A resin molded product was obtained in the same manner as in. The appearance of this molded product was good.

A weather resistance test was conducted on the obtained molded product in the same manner as in Example 1. After the test, no cracking or resin deterioration was observed on the surface of the molded product, and the weather resistance was good.

[Example 3] In the production process of the component (A), 70 parts of methyl methacrylate was changed to 69 parts, 24 parts of n-butyl acrylate was changed to 27 parts, and 6 parts of glycidyl methacrylate was changed to 4 parts of methacrylic acid. Except for the above, an emulsion for glass fiber sizing agent was prepared in the same manner as in Example 1, and a glass fiber sizing agent was obtained using this emulsion for glass fiber sizing agent. No generation of aggregates was observed in the glass fiber sizing agent compounding and preparing process, and the compounding state was stable.

A glass fiber bundle was obtained in the same manner as in Example 1 except that this glass fiber sizing agent was used. The present glass fiber bundle was in a well-focused state, and the cutability of the fiber bundle was also good.

Example 1 except that this glass fiber bundle was used
A resin molded product was obtained in the same manner as in. The appearance of this molded product was good.

A weather resistance test was conducted on the obtained molded product in the same manner as in Example 1. After the test, no cracking or resin deterioration was observed on the surface of the molded product, and the weather resistance was good.

Example 4 A glass fiber bundle was prepared in the same manner as in Example 1 except that the amount of methyl methacrylate was changed to 48 parts and the amount of n-butyl acrylate was changed to 46 parts in the production process of the component (A). Make an emulsion for the agent,
A glass fiber bundle was obtained using this emulsion for glass fiber sizing agents. No generation of aggregates was observed in the glass fiber sizing agent compounding and preparing process, and the compounding state was stable. Again 7
It was stable even after being left for a day, and neither aggregates nor precipitates were found.

The present glass fiber bundle was in a good bundled state, and the cutting processability of the fiber bundle was also good.

Example 1 except that this glass fiber bundle was used
A resin molded product was obtained in the same manner as in. The appearance of this molded product was good.

A weather resistance test was conducted on the obtained molded product in the same manner as in Example 1. After the test, no cracking or resin deterioration was observed on the surface of the molded product, and the weather resistance was good.

[Example 5] In the manufacturing process of the component (A), the amount of methyl methacrylate was changed to 75 parts, the amount of butyl acrylate was changed to 25 parts, the amount of glycidyl methacrylate was changed to 0 part, and the amount of octyl mercaptan was changed to 0 part. A glass fiber sizing agent emulsion was prepared in the same manner as in Example 1 except for the above, and a glass fiber sizing agent was obtained using this glass fiber sizing agent emulsion. No generation of aggregates was observed in the glass fiber sizing agent compounding and preparing process, and the compounding state was stable. Further, it was stable even after standing for 7 days, and neither aggregates nor precipitates were observed.

The present glass fiber bundle was in a good bundled state, and the cutability of the fiber bundle was also good.

Example 1 except that this glass fiber bundle was used
A resin molded product was obtained in the same manner as in. The appearance of this molded product was good.

A weather resistance test was conducted on the obtained molded product in the same manner as in Example 1. After the test, no cracking or resin deterioration was observed on the surface of the molded product, and the weather resistance was good.

Example 6 An emulsion for a glass fiber sizing agent was prepared in the same manner as in Example 1 except that methacrylamide was used instead of acrylamide as the monomer component used for preparing the component (B). A glass fiber sizing agent was obtained using this emulsion for a glass fiber sizing agent. No generation of aggregates was observed in the glass fiber sizing agent compounding and preparing process, and the compounding state was stable.

The present glass fiber bundle was in a good bundled state, and the cutability of the fiber bundle was also good.

Example 1 except that this glass fiber bundle was used
A resin molded product was obtained in the same manner as in. The appearance of this molded product was good.

A weather resistance test was conducted on the obtained molded product in the same manner as in Example 1. After the test, no cracking or resin deterioration was observed on the surface of the molded product, and the weather resistance was good.

Comparative Example 1 Pure water 150 was placed in a reaction vessel equipped with a cooling pipe, a thermometer, a stirrer, a dropping device, and a nitrogen introducing pipe.
Part, polyvinyl alcohol (Kuraray Co., Ltd., degree of polymerization: 5
00) 5 parts were charged, and while stirring in a nitrogen atmosphere, 8
The temperature was raised to 0 ° C. After confirming that the internal temperature reached 80 ° C., 0.3 part of potassium persulfate was added as a polymerization initiator and held for 15 minutes. Subsequently, 70 parts of methyl methacrylate, 24 parts of n-butyl acrylate, 6 parts of glycidyl methacrylate, 1 part of octyl mercaptan as a chain transfer agent, sodium dialkylsulfosuccinate as a surfactant (Kao Corporation, trade name “Perex OT
-P ") 1 part of the mixture was added dropwise to the reaction vessel over 4 hours, emulsion polymerization was carried out in the presence of polyvinyl alcohol, and the temperature was kept at 80 ° C for 1 hour and then cooled to room temperature to carry out emulsion polymerization. Upon completion, an emulsion was obtained.

Then, a glass fiber sizing agent was obtained in the same manner as in Example 1 except that this emulsion was used. No generation of agglomerates was observed in this step, and the composition was in a stable state. However, when the glass fiber sizing agent was allowed to stand for 3 days, precipitation was observed.

Next, this glass fiber sizing agent was applied to glass fibers and bundled in units of 200 glass fibers were heat treated at 140 ° C. for 12 hours to obtain glass fiber bundles. Was bad and could not be cut with the cutter of the SMC machine.

This glass fiber bundle was manually cut with scissors to produce a sheet molding compound in the same manner as in Example 1. Subsequently, a resin molded product was obtained in the same manner as in Example 1. The appearance of this molded product was good.

A weather resistance test was conducted on the obtained molded product in the same manner as in Example 1. After the test, a slight crack was found on the surface of the molded product, and the weather resistance was slightly poor.

[Comparative Example 2] 150 parts of pure water was charged into a reaction vessel equipped with a cooling tube, a thermometer, a stirrer, a dropping device, and a nitrogen introducing tube, and the temperature was raised to 80 ° C while stirring under a nitrogen atmosphere. . After confirming that the internal temperature reached 80 ° C., 0.3 part of potassium persulfate was added as a polymerization initiator and held for 15 minutes. Subsequently, 70 parts of methyl methacrylate, n-
A mixture of 24 parts of butyl acrylate, 6 parts of glycidyl methacrylate, 1 part of octyl mercaptan as a chain transfer agent, and 5 parts of polyoxyethylene oleyl ether (trade name "Emulgen 404" manufactured by Kao Corporation) as a surfactant for 4 hours. Then, the mixture is dropped into a reaction vessel, emulsion polymerization is carried out, the temperature is kept at 80 ° C. for 1 hour and then cooled to room temperature to end the emulsion polymerization, and the component (A) (methyl methacrylate / n-butyl acrylate / glycidyl methacrylate) is added. An emulsion containing a copolymer) was obtained.

Next, a glass fiber sizing agent was prepared in the same manner as in Example 1 except that this emulsion was used. No agglomerates were generated in this step, and the composition was stable, but when the glass fiber sizing agent was left standing for 3 days, a precipitate was observed.

Next, this glass fiber sizing agent was applied to glass fibers and bundled in units of 200 glass fibers were heat treated at 140 ° C. for 14 hours to obtain glass fiber bundles. Was bad and could not be cut with the cutter of the SMC machine.

The glass fiber bundle was manually cut with scissors to produce a sheet molding compound in the same manner as in Example 1. Subsequently, a resin molded product was obtained in the same manner as in Example 1. The appearance of this molded product was good.

A weather resistance test was conducted on the obtained molded product in the same manner as in Example 1. After the test, no cracking or resin deterioration was observed on the surface of the molded product, and the weather resistance was good.

[Comparative Example 3] A nonionic surfactant (manufactured by Sanyo Kasei Co., Ltd., trade name "Noniball 400") was placed in a reaction vessel equipped with a cooling tube, a thermometer, a stirrer, a dropping device and a nitrogen introducing tube.
40 g, polyvinyl alcohol (saponification degree 73 mol%,
150 g of aqueous solution (concentration 20%) having a degree of polymerization of 500), 3 g of potassium persulfate, 1.5 g of acetic acid, 0.7 g of sodium acetate,
Pure water (1000 g) and vinyl acetate (100 g) were charged, the rotation speed was adjusted to 200 rpm, and the temperature was raised to 50 ° C.

Then, when the addition of the 5% Rongalite aqueous solution was started, an increase in the internal temperature was observed after about 10 minutes. At this point, the polymerization was started, and the addition of vinyl acetate was started.
900 g of vinyl acetate was continuously added over time. On the other hand, 5%
25 g of the Rongalit aqueous solution was added in the meantime, and after the addition of vinyl acetate was completed, 5 g was continuously added to make the residual monomer 0.5% or less.

Then, a glass fiber sizing agent was obtained in the same manner as in Example 1 except that the emulsion thus obtained was used.

Although the present glass fiber bundle was in a good bundled state, the cutting processability of the fiber bundle was poor and it could not be cut with the cutter of the SMC machine.

Next, a sheet molding compound was produced in the same manner as in Example 1 except that this glass fiber bundle was used, and a resin molded product was obtained using this compound. Some relief of glass fiber traces was seen.

A weather resistance test was carried out on the obtained molded product. As a result, cracks were running along the glass fiber on the surface of the molded product after the test, and the weather resistance was poor.

Tables 1 and 2 show the components (A) and (B) in the above Examples and Comparative Examples, and the evaluation results of each example.

[0165]

[Table 1]

[0166]

[Table 2]

[0167]

As is apparent from the above description, according to the present invention, (meth) acrylic polymer particles (component (A))
By blending and preparing a glass fiber sizing agent having excellent sizing properties and stability, by using an emulsion for a glass fiber sizing agent containing a water-soluble polymer (component (B)) containing a (meth) acrylamide unit. By using this glass fiber sizing agent, a glass fiber bundle having excellent cutting workability can be produced. Further, according to the present invention using this glass fiber bundle, it is possible to produce a resin molded product having good appearance and weather resistance.

[Brief description of drawings]

FIG. 1 is a schematic diagram showing an SMC machine used in the present invention.

[Explanation of symbols]

1 resin mixture 2 Release film 3 coaters 4 glass fiber bundle 5 cutter 6 rolling rollers 7 Take-up roller

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) // C08L 101: 00 D06M 101: 00 D06M 101: 00 C03C 25/02 NF term (reference) 4F072 AA02 AA04 AA05 AA07 AA08 AB09 AB22 AC05 AD04 AD09 AD13 AD23 AD37 AD38 AD41 AD44 AL02 AL04 AL06 AL07 4G060 BA01 BB02 BC01 CB09 CB12 4L033 AA09 AB01 AC12 CA18 CA23

Claims (12)

[Claims] 1. An emulsion for a glass fiber sizing agent, which comprises (meth) acrylic polymer particles and a water-soluble polymer containing a (meth) acrylamide unit. 2. The emulsion for a glass fiber sizing agent according to claim 1, which is obtained by polymerizing at least a (meth) acrylic monomer in the presence of a water-soluble polymer containing a (meth) acrylamide unit. 3. The emulsion for glass fiber sizing agent according to claim 1, wherein at least a (meth) acrylic monomer is polymerized in the presence of a water-soluble polymer containing a (meth) acrylamide unit. Manufacturing method. 4. A glass fiber sizing agent containing the emulsion according to claim 1. 5. A glass fiber bundle formed by applying the glass fiber sizing agent according to claim 4. 6. A resin composition containing the glass fiber bundle according to claim 5. 7. The resin composition according to claim 6, which contains a (meth) acrylic resin. 8. The resin composition according to claim 6, which is a sheet molding compound. 9. The resin composition according to claim 6, wherein the resin composition is a bulk molding compound. 10. A resin molded product containing the glass fiber bundle according to claim 5. 11. The resin molded product according to claim 10, which contains a (meth) acrylic resin as a matrix resin. 12. A method for producing a resin molded product, which comprises mixing the glass fiber bundle formed by applying the glass fiber sizing agent according to claim 4 with a resin or a resin composition and molding the mixture.