JP3821169B2 - Anti-fraying adhesive for glass fiber yarns or woven fabrics - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention is a glass fiber yarn or fabric (together both also referred to as "glass fiber fabric") related to raveling-preventing agent, glass fiber yarn used as the printed circuit board in a form is especially impregnating the resin varnish or about the raveling-preventing agent of the woven fabric.
[0002]
[Prior art]
As described in JP-A-6-341065, JP-B-2-23626, and the like, glass fiber fabrics were mostly woven by a shuttle loom in the past. The ratio of those woven by a plain loom such as an air jet loom is increasing due to efficiency and good quality. In such a weaving loom, the weft is cut at each weft insertion, unlike the weaving loom, in which the weft is folded at the end of the fabric to form an adjacent weft. In addition, the cut ends of the wefts are present in a tuft shape. Most glass fiber fabrics are used for printed circuit boards. At that time, they are impregnated with a thermosetting resin varnish such as an epoxy resin and then dried to form a prepreg. When a glass fiber fabric woven by an air jet loom as described above and impregnated with a resin varnish as described above is impregnated with a large amount of varnish and the weft is not folded back, Fraying easily causes troubles such as winding around the roll in the impregnation process. Since the end portion is cut, the fraying is more likely to occur if the length of the ear portion is shortened from an economical point of view. In addition, even a woven fabric woven with a knot loom may be used in two or three parts. In this case, too, when the machine is simply mechanically cut, the warp can be easily removed from the cut part. Start fraying.
[0003]
[Problems to be solved by the invention]
In order to prevent such fraying, it has been studied to cut the end or ground of the woven fabric while melting and bonding the glass yarn with a laser beam. However, the melt adhesion is weak and it is easily bonded to strong ironing. There are drawbacks such as peeling off of the part or melting glass forming a fine sphere and falling into the varnish bath during the resin varnish impregnation process, and is not a complete countermeasure.
In addition, attempts have been made to prevent fraying by applying hot melt adhesive to edges and cuts, but if the adhesive dissolves into various organic solvents used in resin varnishes, the performance of the varnish will be affected. There is a fear. In particular, in glass fiber fabrics for impregnating varnish used in fields requiring high quality assurance such as printed circuit boards, it is essential that the adhesive does not elute. However, conventionally used ethylene-vinyl acetate copolymers or copolymers based on polyamides obtained from polymerized fatty acids and aliphatic amines have insufficient solvent resistance and cannot be used as adhesives. is there.
In addition, attempts have been made to use thermosetting resins such as epoxy resins and phenolic resins as adhesives, but thermosetting resins have good chemical resistance, but until they are cured after being applied to glass fiber fabrics. It takes time and is not satisfactory in terms of equipment and productivity.
Furthermore, a thermoplastic resin was tried as an adhesive, but the melt viscosity was high and impregnation was insufficient, and there was a risk of fluffing of glass yarn from the cut part, and the woven fabric thickness of the coated part became thicker than other parts, When the glass fiber fabric is wound on a roll, troubles such as so-called “ear height” occur.
[0004]
Furthermore, as described in the above Japanese Patent Publication No. 23-26626, conventionally used adhesives such as ethylene-vinyl acetate copolymer have an open time when applied in the form of an organic solvent solution. There is a drawback that is long. That is, when a commonly used adhesive solution such as ethylene-vinyl acetate copolymer is applied to a glass fiber fabric, the solution does not easily solidify, and the adhesive retains tack for a long time. There is a problem in that adjacent glass fiber fabric layers adhere to each other when wound on.
[0005]
[Means for Solving the Problems]
As a result of intensive studies in view of the present state of the technology related to the fraying of such glass fiber fabrics, the present inventors have found that it is very effective to apply an active energy ray-curable resin composition, and the present invention. It came to complete.
[0006]
That is, according to 1st invention, the active energy ray containing urethane (meth) acrylate formed by making the diisocyanate chosen from aromatic, aliphatic, and alicyclic and lactone modified | denatured 2-hydroxyethyl (meth) acrylate react. An anti-fraying fixing agent for glass fiber yarns or woven fabrics comprising a curable resin composition is provided.
According to the second invention, the glass fiber of the first invention, wherein the urethane (meth) acrylate is obtained by reacting tolylene diisocyanate or isophorone diisocyanate with ε-caprolactone-modified 2-hydroxyethyl (meth) acrylate. An anti-fraying adhesive for yarns or woven fabrics is provided.
According to the third invention, a diisocyanate selected from aromatic, aliphatic and alicyclic, a lactone polyester polyol, and a (meth) acrylate monomer having at least one hydroxyl group in one molecule are reacted. An anti-fraying fixing agent for glass fiber yarn or woven fabric comprising an active energy ray-curable resin composition containing urethane (meth) acrylate is provided.
According to the fourth invention, the glass fiber yarn of the third invention, wherein the urethane (meth) acrylate is obtained by reacting tolylene diisocyanate or isophorone diisocyanate with polycaprolactone and 2-hydroxyethyl (meth) acrylate. Or an anti-fraying adhesive for woven fabrics is provided.
The present invention will be described in detail below.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
The glass fiber fabric used in the present invention is not particularly limited to the weaving method, thickness, glass fiber weight per unit area, presence or absence of a sizing agent, and the like.
[0008]
The active energy ray-curable resin composition used in the present invention is not particularly limited as long as it is cured with active energy rays, and examples thereof include those described below.
[0009]
(Example of active energy ray-curable resin composition)
Examples of the active energy ray curable resin composition which can be used in the present invention, (1) a urethane (meth) acrylate oligomers such as preparative (A), or with these, styrene is an optional component, (meth) acrylonitrile , (Meth) acrylic acid ester and other monomers (described later dilution monomer) (B).
[0010]
(1) As urethane (meth) acrylate,
(1-a) an organic isocyanate, and (1-b) a reaction product obtained by reacting a (meth) acrylate monomer having at least one hydroxyl group in one molecule by a known method, or (1- In addition to the components a) and (1-b), (1-c) is a reaction product obtained by reacting a polyol having two or more hydroxyl groups in one molecule by a known method.
[0011]
Here, examples of organic isocyanates include aromatic, aliphatic and alicyclic diisocyanates such as tolylene diisocyanate, 4,4-diphenylmethane diisocyanate, 1,6-hexamethylene diisocyanate, xylylene diisocyanate, and isophorone diisocyanate.
[0012]
Examples of the (meth) acrylate monomer having at least one hydroxyl group in one molecule include lactone-modified 2-hydroxyethyl (meth) acrylate.
[0013]
Furthermore, examples of the polyol having two or more hydroxyl groups in one molecule include lactone polyester polyols such as polycaprolactone and polybutyrolactone.
[0014]
As an example of the known method herein, the reaction temperature is preferably 60 to 90 ° C. at normal pressure, and it is generally desirable to use a catalyst for promoting the reaction. Typical examples of the catalyst include dibutyltin dilaurate, dibutyltin diethylhexoate, dibutyltin sulfide, dibutyltin dibutoxide and the like. Such a catalyst effective for the reaction between a hydroxyl group and an isocyanate group is preferably 50 to 5000 ppm, particularly preferably 250 to 1000 ppm. The reaction is usually carried out until the concentration of residual isocyanate is below a predetermined concentration.
[0015]
In the present invention, any ethylenically unsaturated monomer (hereinafter referred to as a dilution monomer) can be used in order to adjust the viscosity of the composition and improve the physical properties as a fraying prevention sticker.
Specific examples of the dilution monomer include styrene, (meth) acrylonitrile, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, 2- Chlorostyrene, phenoxyethyl (meth) acrylate, (meth) acrylic acid, 2-hydroxyethyl (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri ( Examples thereof include (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol hexa (meth) acrylate. These dilution monomers can be used alone or in combination of two or more.
[0016]
Furthermore, the active energy ray-curable resin composition used in the present invention can be cured with active energy rays such as ultraviolet rays and electron beams, but when it is cured with ultraviolet rays, a photopolymerization initiator is used. It is also possible to use a photopolymerization initiation aid together if necessary.
[0017]
Examples of the photopolymerization initiator include benzoin, benzoin methyl ether, benzoin isopropyl ether, acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1- Hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, N, N -Dimethylaminoacetophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, 2-aminoanthraquinone, 2,4-diethylthioxanthone, 2, - diisopropyl thioxanthone, acetophenone dimethyl ketal, methyl benzophenone, 4,4'-dichlorobenzophenone, 4,4'-bisdiethylaminobenzophenone, Michler's ketone, and the like. These can be used alone or in combination of two or more. Further, as such a photopolymerization initiator, a known and commonly used photopolymerization initiator assistant such as N, N-dimethylaminobenzoic acid ethyl ester, triethanolamine or triethylamine may be used alone or in combination of two or more. Can do. The content of the photopolymerization initiator is preferably in the range of 1 to 10 parts by weight, particularly 3 to 6 parts by weight with respect to 100 parts by weight of the composition.
[0018]
The active energy ray-curable composition as exemplified above can be cured by irradiation with active energy rays.
Examples of active energy rays that can be used include ultraviolet rays and electron beams.
The irradiation conditions when ultraviolet rays are used are preferably a mercury lamp, a metal halide lamp, etc., and the curing energy is preferably ²⁰ to 500 mJ / cm ² . Moreover, it is also possible to irradiate ultraviolet rays to both surfaces of the glass fiber fabric which is a base material as needed. Moreover, it is preferable that the irradiation conditions at the time of using an electron beam are the irradiation amount of 1-5 Mrad with the acceleration voltage 150-250 keV. The electron beam irradiation is performed in a nitrogen atmosphere.
[0019]
【Example】
EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.
[0020]
[Synthesis Example 1]
In a reaction vessel immersed in an oil bath and equipped with a stirrer, thermometer, addition funnel and dry air supply port, 348 g (2 mol) of 2,4-tolylene diisocyanate (TDI), dibutyltin dilaurate (DBTDL) 0. 5 g was charged and the temperature was raised. When the inside of the reaction vessel reached 70 ° C., 688 g (2 mol) of ε-caprolactone-modified 2-hydroxyethyl acrylate (Placcel FA-2, molecular weight 344, manufactured by Daicel Chemical Industries, Ltd.) was added from the addition funnel. . After completion of the addition, the mixture was aged until the residual diisocyanate concentration was 0.1% by weight or less to obtain urethane acrylate (Synthesis Example 1).
[0021]
[Synthesis Example 2]
A urethane acrylate (Synthesis Example 2) was obtained in the same manner as in Synthesis Example 1, except that 444 g (2 mol) of isophorone diisocyanate (IPDI) was used instead of TDI in Synthesis Example 1.
[0022]
[Synthesis Example 3]
In a reaction vessel immersed in an oil bath and equipped with a stirrer, thermometer, addition funnel and dry air supply port, 348 g (2 mol) of 2,4-tolylene diisocyanate (TDI), dibutyltin dilaurate (DBTDL) 0. 5 g was charged and the temperature was raised. When the inside of the reaction vessel reached 70 ° C., 530 g (1 mol) of polycaprolactone (Placcel 205, polycaprolactone diol having a molecular weight of 530, manufactured by Daicel Chemical Industries, Ltd.) was added from the addition funnel. After completion of the addition, the temperature in the reaction vessel was kept at 70 ° C. until the residual diisocyanate concentration reached the theoretical value to produce a polycaprolactone urethane prepolymer. Thereafter, after the addition of 232 g (2 mol) of 2-hydroxyethyl acrylate (HEA), the reaction vessel was kept at 70 ° C. until it was confirmed that the isocyanate concentration in the sample withdrawn from the reaction product was 0.1% by weight or less. The aging was carried out. As a result, a urethane acrylate oligomer (Synthesis Example 3) was obtained.
[0023]
[Synthesis Example 4]
A urethane acrylate oligomer (Synthesis Example 4) was obtained in the same manner as in Synthesis Example 3 except that TDI in Synthesis Example 3 was changed to 444 g (2 mol) of isophorone diisocyanate (IPDI).
[0024]
(Examples 1-4)
An anti-fraying fixing agent for a glass fiber fabric comprising an active energy ray-curable resin composition having a composition as shown in Table 1 (numerical values represent parts by weight) was prepared. The obtained anti-fraying adhesive was applied to a glass fiber fabric (plain weave, thickness 200 μm) by a roller coater along the warp direction with a width of 10 mm, and then a high-pressure mercury lamp (irradiation conditions 120 W / cm × 50 m / min × 1). Cured by pass). The application amount was 100 g / m ² .
[0025]
[Table 1]
[0026]
Cut the central part of the glass fiber fabric obtained above with the anti-fraying adhesive applied along the warp, measure the tensile bond strength with one warp at the end, g). Also, the glass fiber woven fabric coated with anti-fraying agent obtained above is immersed in various solvents for 72 hours (25 ° C), and the state of the anti-fraying agent-coated portion is observed to evaluate the solvent resistance (O: change) △: Swelled, ×: Warp frayed). Further, the glass fiber fabric was bent, and the flexibility of the application part of the anti-fraying adhesive was evaluated (◯: good flexibility, x: poor flexibility). These results are shown in Table-2.
In addition, about the obtained fraying prevention fixing agent application | coating glass fiber fabric, a prepreg was produced, it cut | disconnected to a fixed dimension (30 cm), and as a result of stacking, the difference in the height of an edge part and a center part was hardly seen. It was.
[0027]
[Table 2]
[0028]
【The invention's effect】
The fray-preventing fixing agent of the present invention has a long pot life at normal temperature and a short time for curing with active energy rays, and therefore has excellent handleability and productivity when applied to glass fiber fabrics. Further, the glass fiber woven fabric coated with the anti-fraying fixing agent of the present invention has a high fraying strength at the portion where the anti-fraying fixing agent is applied, and is excellent in solvent resistance against various solvents. Moreover, since the coating film has a softness | flexibility in the applied part, it is not cracked or broken at the time of handling. Even when a large number of glass fiber fabrics are stacked as a prepreg, there is almost no difference in height, and the cut ends are kept straight.

Claims (4)

Glass fiber yarn comprising an active energy ray-curable resin composition containing urethane (meth) acrylate obtained by reacting diisocyanate selected from aromatic, aliphatic and alicyclic and lactone-modified 2-hydroxyethyl (meth) acrylate Or anti-fraying adhesive for woven fabrics. The glass fiber yarn or woven fabric anti-fraying fixing agent according to claim 1, wherein the urethane (meth) acrylate is obtained by reacting tolylene diisocyanate or isophorone diisocyanate with ε-caprolactone-modified 2-hydroxyethyl (meth) acrylate. . Active energy containing urethane (meth) acrylate obtained by reacting diisocyanate selected from aromatic, aliphatic and alicyclic, lactone polyester polyol, and (meth) acrylate monomer having at least one hydroxyl group in one molecule An anti-fraying fixing agent for glass fiber yarns or woven fabrics comprising a linear curable resin composition. The glass fiber yarn or woven fabric anti-fraying fixing agent according to claim 3, wherein the urethane (meth) acrylate is obtained by reacting tolylene diisocyanate or isophorone diisocyanate with polycaprolactone and 2-hydroxyethyl (meth) acrylate.