JPH0477694B2 - - Google Patents

Description

[Detailed description of the invention]

[Object of the Invention] (Industrial Application Field) The present invention relates to a binder for glass fibers. (Prior Art) Glass fiber bundles are produced by collecting glass fibers drawn from a bushing and winding them on a mandrel rotating at high speed, preferably by heating,
Used dry. Glass fiber bundle manufacturing process or subsequent unwinding;
A binder is added to glass fibers in order to prevent fuzz from occurring during secondary processing steps such as alignment, cutting, and twisting, to protect the surface of the glass fibers, and to provide cohesiveness. As a binder, an aqueous solution containing a film forming agent, a lubricant, and a coupling agent is usually used, but such glass fiber bundles tend to generate static electricity during the secondary processing process, so to prevent this, an antistatic agent is added to the binder. need to be added. (Problems to be solved by the invention) As antistatic agents, ammonium chloride, quaternary
Class ammonium salts are known, but when ammonium chloride is used, glass fiber bundles obtained by adding this binder are used as reinforcing fibers.
Problems such as decreased boiling resistance of FRP are likely to occur,
Furthermore, when a quaternary ammonium salt is used, there is a problem in that the glass fiber bundle tends to be colored. The present invention aims to solve the problems of the prior art described above. [Structure of the invention] (Means for solving the problems) The present invention has been made to solve the above-mentioned problems, and the general formula

A binder for glass fibers, characterized by containing a compound represented by the formula: However, R ₁ is a C ₁ to C ₂₀ alkyl group or C ₆ H ₅ ,
R ₂ is a C ₁ to C ₄ alkyl group, C ₆ H ₅ or
CH ₆ H ₅ CH ₂ , R ₃ and R ₄ are C ₁ to C ₄ alkyl groups,
C ₆ H ₅ or (C ₂ H ₄ O)-nH (n = 1 to 5), X ^- has the general formula R ₅ SO ₄ ^- , R ₅ R ₆ PO ^- or
A compound represented by R ₅ OR ₆ OPO ₂ ^- , where R ₅ and R ₆ represent a C ₁ to C ₄ alkyl group. Next, the present invention will be explained in more detail. In the present invention, a binder (hereinafter referred to as the present binder) containing a compound represented by the above-mentioned general formula (hereinafter referred to as the present compound) is used. R ₁ in the above general formula is CH ₃ , C ₂ H ₅ , C ₃ H ₇
Lower alkyl groups such as, or alkyl groups with a larger number of carbon atoms such as C ₄ H ₉ , C ₅ H ₁₁ , C ₁₆ H ₃₃ , C ₁₈ H ₃₇ ,
A saturated linear alkyl group such as or an unsaturated linear alkyl group, or C ₆ H ₅ or C ₆ H ₅ CH ₂ can be used, but in particular C 4 or higher, preferably C 4 to 18
It is preferable to use a straight chain alkyl group or C ₆ H ₅ , which reduces hydrophilicity as described below and improves FRP,
Increases compatibility with resins used in FTP,
Boiling resistance can be further improved. Note that the above alkyl group may have a branch. R ₂ is a C ₁ to C ₄ straight chain alkyl group or C ₆ H ₅
It is preferable to use R ₃ and R ₄ are C ₁ to C ₄ alkyl groups, C ₆ H ₅ ,
or _C6H5 - _{CH2 ,} ( _CH2H4O )-nH ( _n =1-5)
However, it is preferable to use a _C1 - _C4 straight chain alkyl group _{or C6H5} . As R ₅ and R ₆ , it is desirable to use a C ₁ to C ₄ straight chain alkyl group. Note that R ₃ , R ₄ or R ₅ , R ₆ do not necessarily have to be the same, and different groups can also be used. Regarding the composition of the sizing agent to which the present compound is added, a commonly used sizing agent can be appropriately selected and used depending on the use of the glass fiber bundle to which the sizing agent is added and bundled. In the present invention, coupling agents such as acrylic silane and aminosilane are preferably used in an amount of 0.01 to 5 wt%, preferably 0.1 to 1.0 wt%,
1 to 15 wt%, preferably 2 to 10 wt% of a film forming agent such as polyvinyl acetate emulsion as a solid content,
Lubricant such as nonionic surfactant as solid content
An example is a sizing agent containing 0.01 to 2 wt%, preferably 0.2 to 1.0 wt%. The amount of this compound to be added to the binder is 0.01~
A suitable amount is 5wt%, preferably 0.1 to 2wt%. If this amount is too small, the antistatic effect will not be sufficient, and if this amount is too large, the antistatic effect will not increase significantly, and conversely, the cohesiveness of the glass fibers will tend to deteriorate. The glass fiber to which this binder should be applied is as follows:
Glass fibers with a diameter of 3 to 25 μm, preferably 9 to 16 μm are suitably used, and the present sizing agent is added to the glass fibers according to a conventional method, and about 50 to 5,000 fibers are bundled to form a glass fiber bundle, preferably heated and dried. It can be used to reinforce FRP, FTP, etc. There are no particular limitations on the type of resin that should be used for the above FRP and FTP, but thermosetting resins such as unsaturated polyester resins, epoxy resins, and phenol resins, and thermoplastic resins such as PP, PBT, nylon, and PC may be used. When used, particularly excellent effects can be obtained. The amount of the binder to be added is suitably 0.3 to 3 wt%, preferably 0.5 to 2 wt%, based on the solid content of the glass fibers. (Function) This compound dissociates into ions, imparts conductivity _to the glass fiber bundle using this binder, and prevents charging _.
etc., so it has low hydrophilicity and is compatible with the resins used for FRP and FTP,
Prevents deterioration of FTP's boiling resistance. Further, by using a long-chain alkyl group (preferably having 4 to 18 carbon atoms), the lubricity of the present binder is enhanced and the glass fiber bundle using the present binder is prevented from becoming fluffy. In addition, this compound has a counter ion bonded to ^N
It is thought that this suppresses the reaction with N ⁺ and thus prevents the formation of colored reaction products during heating and drying. Example 1 C ₁₈ H ₃₇・C ₂ H ₅・(CH ₃ ) ₂ N ⁺・C ₂ H ₅ S ₄ O ⁻
Contains 0.3wt%, 0.2wt% γ-methacryloquinepropyltrimethoxysilane as a coupling agent, 0.5wt% nonionic surfactant as a lubricant, and 6wt% solid content of polyvinyl acetate emulsion as a film forming agent. A sizing agent was added as a solid content of 1.5wt% to 13μ glass fibers drawn from the bushing according to a conventional method, and 200 fibers were bundled and wound.
The heated and dried strands were heated using a static honest meter at an applied voltage of 8 kV and a temperature of 25°C.
Charge voltage and half-life were measured at 50% humidity. In addition, 30 parts by weight of the above glass fiber bundle was added with a resin composition mainly composed of unsaturated polyester resin (40 wt% resin, 55 wt% filler, pigment, curing agent, etc. in the composition).
Add 100 parts by weight of 5wt%), impregnate, and heat to 140℃.
After heating and curing for 3 minutes, a sheet-like test piece (size 5 cm x 5 cm, thickness 3
mm) were cut out and boiled to examine changes in appearance. The above results are shown in the attached table. Example 2 C ₁₂ H ₂₅ · CH ₃ · (C ₂ H ₄ O) - ₂ H · (C ₂ H ₄ O) - ₂ H · in place of this compound in Example 1
The results of a test similar to that of Example 1 using N ⁺ (CH ₃ ) ₂ PO ^- are shown in the attached table. Comparative Example 1 C ₁₂ H ₂₅ in place of this compound in Example 1
The results of a test similar to Example 1 using (CH ₃ ) ₃ N ⁺ Cl ^- are shown in the attached table. Comparative Example 2 The same test as in Example 1 was conducted using NH ₄ Cl in place of the present compound in Example 1. The results are shown in the attached table. Comparative Example 3 The results of a similar test using a binder having the same content of other components as in Examples 1, 2, and Comparative Example and containing no antistatic agent are shown in the attached table.

【table】

[Table] ○: No change in appearance △: Slight blister formation ×: blister all over the surface
Occurrence (Effect) The antistatic performance is equivalent to or higher than that of quaternary ammonium salts, and there is no reduction in boiling resistance or coloring.

Claims (1)

[Scope of Claims] 1. A binder for glass fibers, characterized by containing a compound represented by the general formula [Formula]. However, R ₁ is a C ₁ to C ₂₀ alkyl group or C ₆ H ₅ ,
_R2 is _{a C1} to _C4 alkyl group _{, C6H5} or _{C6H5CH2 ,}
R ₃ and R ₄ are C ₁ to C ₄ alkyl groups, C ₆ H ₅ or (C ₂ H ₄ O)-nH (n = 1 to 5), X ^- is the general formula R ₅ SO ₄ ^- , R ₅ R ₆ PO ^-or
A compound represented by R ₅ OR ₆ OPO ₂ ^- , where R ₅ and R ₆ are C ₁ to C ₄ alkyl groups.