JPS5837322B2 - UV curable resin composition - Google Patents

Description

[Detailed description of the invention] The present invention relates to an ultraviolet curable resin composition.

Conventionally, ultraviolet curable resin compositions have been used for industrial purposes such as paints,
It is used to form thin film cured resin layers for printing inks, adhesives, etc.

In addition, highly transparent reinforcing fillers such as glass fibers are added to unsaturated polyester resin or epoxy acrylate resin, and the composite material is cured by ultraviolet light in the form of a slightly thick paste or sheet. is also being carried out.

However, these resins can be cured in a short time when formed into a relatively transparent thin-walled article with a thickness of about 0.1 to 0.2 inches or less; In the case of meat moldings or opaque paste materials containing fillers such as talc, glass powder, and glass milled fibers, the transmission of ultraviolet rays becomes poor, resulting in a slow reaction rate and, therefore, extremely slow curing on the side opposite to the exposure. However, when the thickness of the film increases, it hardly hardens.

Therefore, the present invention aims to solve the drawbacks of conventional ultraviolet curable resins, such as poor curing of thick molded products or thick film coatings. Thick film coating, which was previously difficult,
It can effectively cure thick molded products with ultraviolet light in a short time, and has excellent workability such as wire cross-talk and coating properties.It also lowers the mechanical strength of composite materials when used in combination with glass fiber. It has the characteristics that it never happens.

The present invention will be specifically explained below.

First, the ultraviolet curable resin composition of the present invention is composed of an ultraviolet curable resin compound (4) shown below and glass microspheres (B).

(4) UV-curable resin compound.

It contains at least (a) to (c) described below, and the aging (B
When staged) to make sheet resin, the following (
d) and (e).

That is, (a) Ultraviolet curable resin: Usually, polyester resins having ethylenically unsaturated groups, maleated bugene resins, or acrylate resins such as epoxy (meth)acrylate resins and urethane acrylate resins are included.

Further, as the ultraviolet curable resin that can be cured by reacting with a thickener described in (d) below, the unsaturated polyester resin has an active OH group or COOH group at the molecular end or side chain, or Epoxy (meth)acrylate resin or the like is used.

In particular, among these resins, epoxy (meth)acrylate resin has good adhesion to glass microspheres and glass fibers, and therefore has superior physical performance after curing compared to other resins.

(b) Vinyl monomer: Liquid polymerizable monomers such as styrene, vinyltoluene, methyl methacrylate, methyl acrylate, t-butylstyrene, chlorostyrene, diallyl phthalate, or oligomers can be used.

(c) Photosensitizer: Compounds that generate radicals upon irradiation with ultraviolet rays, such as benzoin, benzyl, benzoin methyl ether, penzoin isobutyl ether, penzophenone, and acetophenone, are used.

(d) Thickener: Thickener is used when the above (a) is matured to form a sheet-like structure, and reacts with the active OH groups and COOH groups mentioned in the above (a).

Those that react with OH groups include liquid polyisocyanates such as ISONATE143L and ISONATEI3.
5, PAPI (Kakai Upjohn Co.), CR-200
, CR-300 (Mitsui Nisso Urethane Co., Ltd.), isocyanate compounds such as xylylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, and compounds that react with COOH groups include MgO, Cao
, Mg(OH)2, Ca(OH)2 and other inorganic compounds,
Or there are isocyanate compounds.

(e) Other additives: Various commonly used plasticizers, liquid polymers for imparting flexibility and adhesiveness, such as liquid rubber, as required.
Stabilizers such as liquid xylene resin, stabilizers such as hydroquinone, t-butylcatechol, and benzoquinone for inhibiting colorant thermal polymerization, and polymerization accelerators such as amine compounds can be added.

(B) Glass microspheres Commercially available glass microspheres (glass beads), such as glass plasting beads manufactured by Toshiba Varotech II, etc., are used.

When using glass microspheres with a single particle size distribution, the particle size is usually in the range of 60 to 850μ, preferably 60μ.
~600μ range.

A single particle size distribution here refers to a group of glass microspheres with a particle size in the range of 60 to 850μ, e.g.
It means glass microspheres with a particle size distribution of 0μ.

Therefore, the width of the distribution range can be arbitrarily selected as long as it is within the range of 60 to 850μ.

When the particle size is less than 60 μm, the ultraviolet light transmittance becomes poor, the curing reaction (4) described above becomes slow, and the effect of adding glass microspheres is reduced.

On the other hand, if the particle size is 850 μm or more, the glass spheres are too large, which impairs the workability of coating the resin composition, and the surface of the cured product becomes uneven, resulting in poor surface condition, which is not preferable.

The amount of such glass microspheres (B) added to the above (4) is 30 to 600 parts by weight per 100 parts by weight of (4),
Preferably it is 100 to 400 parts by weight.

If the amount is less than 30 parts by weight, the effect of accelerating the curing rate by adding the glass microspheres is small.

Moreover, if it exceeds 600 parts by weight, the miscibility with (4) and the coating workability after mixing will be poor, and the coating surface will not be smooth.

Next, when using glass microspheres with different particle size distributions, they can be blended as appropriate within the particle size range of 60 to 850 microns.

If the particle size is 60 μm or less and 850 μm or more, problems similar to those when using glass microspheres with a single particle size distribution described above occur, which is not preferable.

However, in terms of the amount added to (4) above, for example, small glass microspheres can be interposed in the voids formed by large glass microspheres, so (4)
30 to iooo parts by weight can be used per 100 parts by weight.

If it is less than 30 parts by weight, the effect of accelerating the curing rate of the resin composition is small, and if it is more than 1,000 parts by weight, the miscibility with the above (4) and coating workability will deteriorate, and the smoothness of the coated surface will be lost.

When such a blend of glass microspheres is used, the particle size of each glass microsphere may be selected so as to achieve close packing, usually within the range of 60 to 850 microns.

For example, the blending ratio is 70 to 4, which is the particle size distribution that includes the largest particle size.
If the range of 30 to 60% by weight of the distribution including the smallest particle size is used with respect to 0% by weight, and the portion of the distribution including the smallest particle size is used for 70% or more, the miscibility with (4) above and the application work will be reduced. It is not preferable because it worsens the sex.

Note that the surface of the glass microspheres is preferably not surface-treated with a coupling agent or the like.

Glass bulbs treated with organic coupling agents commonly used for inorganic materials, such as aminosilane, epoxysilane, vinylsilane, and borane, have the disadvantage of poor light transmission and adversely worsening the curability of the composition. It is from.

By adding such glass microspheres (B) to the above (4) and mechanically stirring, the ultraviolet curable resin composition of the present invention can be easily obtained.

Next, glass fibers are impregnated with the ultraviolet curable resin composition to obtain a prepreg material.

The glass fibers used here are in non-woven and woven forms such as rovings, cut fiber chopped strand mats, surf mats.

When impregnating glass fibers with (4) and (B), (4) and (B) are added in advance according to the amounts added.
) may be used to prepare an ultraviolet curable resin composition and impregnate it into, for example, a glass fiber mat, or alternatively, only the above (4) may be impregnated into two mats, and the two mats may be superimposed. The mats may be overlapped by sprinkling a specified amount of glass microspheres on the contact surface.

By this superposition, the glass microspheres are dispersed into each mat from the contact surface, and (4) and (B) are mixed.

In addition, as mentioned in (4) above, as the ultraviolet curable resin (a) which is a component of (4), active OH groups or CO
An ultraviolet curable resin having an OH group can also be used.

Finally, the method of utilizing the ultraviolet curable resin composition of the present invention will be described.

First, an ultraviolet curable resin containing at least an ultraviolet curable resin (a) having an active OH group or a COOH group, a vinyl monomer (b), a photosensitizer (c) and a thickener (a) is used. Glass fibers are impregnated with the resin composition (4) having a uniform particle size and glass microspheres (B) having a single particle size distribution or different particle size distributions within the range of the particle size distribution and according to the amount added. When heated and aged in a state where ultraviolet rays are blocked, the reaction of the thickener progresses and a B-staged Bripreg sheet is obtained.

Note that (4) and (B) may be mixed in advance, or a method may be adopted in which only (4) is first impregnated and then (B) is sprinkled.

The flexibility, surface tackiness, etc. of this Bripreg sheet can be controlled by changing the amount of thickener added, heat or temperature, and aging time.

In addition, this Bripreg sheet can be stored for a long time at room temperature if it is blocked from ultraviolet rays.

The material to be treated is reinforced or coated with the thus obtained aged Bripreg sheet.

The parts to be treated here refer to parts made of metal, resin, wood, concrete, etc. For example, metal parts may be covered with aged Bripreg sheets, thin parts made of synthetic resin may be reinforced, and ultraviolet rays irradiated. Then, the resin will quickly harden and the thick anti-corrosion lining or laminate reinforcement will be completed.

Curing by ultraviolet rays generates radicals at a higher rate than by heat, and since the resin composition contains glass microspheres, curing can be completed extremely quickly with a small amount of energy.

For the ultraviolet radiation, a commonly used ultraviolet irradiator such as a high-pressure mercury lamp, metal halide lamp, or chemical lamp may be used, or natural light from the sun may be used.

According to the present invention, by including glass microspheres in the resin composition, the transparency of ultraviolet rays is significantly promoted, and as a result, the curing speed of the resin becomes extremely fast, and
It is now possible to effectively perform ultraviolet curing of thick-walled coatings and thick-walled molded products in a short time, which was previously difficult.

In addition, when handling it in paste form as a coating material, glass microspheres are more granular than short glass fibers, glass milled fibers, etc., so they are superior in workability in terms of cross-talk and coating properties. When used as an undercoat paste material, it can effectively smooth the uneven surface of the adherend without prolonging the curing time, and it can be easily hardened.

In addition, the prepreg material of the present invention, in which glass fiber is impregnated with an ultraviolet curable resin and glass microspheres, maintains its mechanical strength as a composite material by using the glass fibers and glass microspheres in combination, and the ultraviolet curing speed can be improved. Available as a fast composite material.

Furthermore, since this prepreg material is solid, it is easy to handle, has little odor, and improves workability.

Furthermore, according to the method of utilizing the ultraviolet curable resin of the present invention,
It is extremely easy to work since it is handled as a aged buripreg sheet and the curing speed is extremely fast as mentioned above.

In addition, by taking advantage of the ability to apply thick coating, it can be widely used as corrosion protection, such as corrosion protection on the external surface of grounding parts of steel tanks and structures, corrosion protection on the external surface of pipelines, piping, cables, etc., steel pipe steel, steel It can be used for heavy corrosion protection of marine structures such as sheet piles, corrosive chemical tanks, and internal corrosion protection of piping. I can do it.

Hereinafter, the present invention will be specifically explained with reference to Examples**.

Example 1 Epoxy acrylate resin / 80 parts by weight Styrene solution Liquid xylene resin (flexibility imparting agent) 20 〃Benzoin isobutyl ether (photosensitizer) 2 〃Erosil (silica filler) 6 liters The above chemicals were thoroughly mixed with a stirrer. Glass microspheres having a particle size of 210 to 300 μm were added in various proportions to 100 parts by weight of the resulting resin composition, and the kneading properties, coating properties, and ultraviolet curability were examined.

The results are shown in Table 1.

The curing time is as follows:
The material was formed into a sheet having a size of about 0.00 x 2.5 mm, was irradiated with ultraviolet rays, and the time required for the back surface to harden was measured.

In addition, the UV irradiation device is EyeCure Light HOI-
L211 (80W/crrL) (manufactured by Eye Graphics) is used, the irradiation distance is 200mm, and the output is 60
It was 0W.

As is clear from Table 1 above, when glass microspheres are added to the ultraviolet curable resin formulation, the curing time is extremely shortened, and thick film coatings of about 2.5% thickness can be coated in 1 to 2 minutes. harden.

Note that if the amount of glass microspheres added is less than 30 parts by weight, the effect of accelerating hardening is small and the coating workability is also poor.

Comparative Example 1 Various fillers such as glass fiber, glass powder, and heavy calcium carbonate were added instead of glass microspheres to 100 parts by weight of the resin compound used in Example 1, and the mixture was improved in kneading properties, coating properties,
Ultraviolet curing properties were investigated.

The curing time measurement method and ultraviolet irradiation device were the same as in Example 1.

The results are shown in Table 2 below. As is clear from Table 2,
When fillers such as surface-treated glass microspheres or glass fibers are added, the crosstalk property does not change much, but the applicability deteriorates and no UV curing accelerating effect is observed.

Example 2 200 parts by weight of various glass microspheres with different early particle sizes were added to 100 parts by weight of the resin composition of Example 1,
The kneading properties, coating properties, and ultraviolet curability of the obtained resin composition were examined.

The results are shown in Table 3. Note that the curing measurement method and ultraviolet irradiation device are the same as in Example 1.

As is clear from Table 3, glass microspheres with a particle size of 60 μm or less have no effect of accelerating hardening and have poor coating properties.

Moreover, in the case of a large particle size of 850 μm or more, coating properties are poor and the surface of the cured product is rough, which is not preferable.

Example 3 Using 100 parts by weight of the liquid resin formulation of Example 1, and in order to confirm the results of Examples 1 and 2, the relationship between the particle size of the glass microspheres and the amount added was evaluated for workability (kneading, (applicability) and curing time were investigated.

The results are shown in Table 4.

The curing measurement method and ultraviolet irradiation device were the same as in Example 1.

As is clear from Table 4, when glass microspheres having a single particle size distribution are used, the particle size can range from 60 to 850 microns and the amount added can range from 30 to 600 parts by weight.

However, if the particle size is 590 to 850 μm and the amount added is 600 parts by weight, the workability becomes poor, which is not preferable.

*Example 4 Table 5 shows the results of using a blend of two types of glass microspheres having different particle size distributions of 590-850μ and 60-180μ.

Note that all other conditions are the same as in Example 3.

From Table 5, when two types of glass microspheres with different particle size distributions are used, the particle size is 60 to 850μ, and the amount added is 3.
It can be used in a range of 0 to iooo parts by weight.

Further, the weight ratio of the part of the particle size distribution including the maximum particle size to the part of the particle size distribution including the minimum particle size is 70/30 to 40/60.

Note that adding 1000 parts by weight of a 40/60 weight ratio is not preferable because workability becomes poor.

Example 5 Epoxy acrylate resin / 80 parts by weight Styrene solution Two glass chopped strand mats were impregnated, glass microspheres were evenly sprinkled on the contact surfaces of the mats, and the surfaces were brought into contact and laminated to form a sandwich structure.

Next, this was left to stand to disperse the glass microspheres in the mat, defoaming it, and then irradiating it with ultraviolet rays to cure it.

Table 6 shows the relationship between the ultraviolet irradiation time and the change in Shore hardness on the back side of the irradiated surface.

As is clear from Table 6, the curing rate increased significantly by adding 30 parts by weight or more of glass microspheres.

Example 6 100 parts by weight of an unsaturated polyester resin monostyrene solution having an active COOH group (Rigolak 150HR BQT manufactured by Showa Kobunshi ■) Magnesium oxide (thickener) 1 〃Benzoin isobutyl ether 2 〃 (photosensitizer) The above chemicals were thoroughly mixed with a stirrer, the resulting resin mixture ioog was weighed, and a plurality of sheets of glass chopped strand mat 400x500% were impregnated into one sheet.

Next, 110 f of glass microspheres of 210 to 300 μm are placed on the surface of the sheet! Sprinkle it evenly, fully disperse it in the glass fiber, and stack the degassed products 1, 2, 3, 4.
．． Six different thicknesses of 5 and 7 ply samples were made.

Each of these samples was sealed with a 120 μm thick black polyethylene film to block ultraviolet rays, and aged in an electric oven at 40° C. for 40 hours to obtain B-staged solid Bripreg sheets.

This sheet was cured by irradiating ultraviolet light under the same conditions as in Example 1.

The relationship between the irradiation time until the back surface of the sheet reaches a pencil hardness of 1H" and the sample thickness is shown by curve X in the figure.

As is clear from this curve X, the sample thickness is about 5. 5
Even in the case of 111 m (7 plies), the hardness of the back surface could be made to a pencil hardness of 1H'' in about 20 minutes.

Comparative Example 2 The same liquid resin formulation Ill as in Example 6 was weighed and mixed into a glass chopped strand mat 400X500%.
1, 2, 3, 4, using one sheet impregnated with
Six different thicknesses of 5 and 7 ply samples were prepared.

Next, this sample was sealed with a black polyethylene film having a thickness of 120 μm, and heated under the same conditions as in Example 6 to obtain a B-staged solid Bripreg sheet.

This sheet was irradiated with ultraviolet rays under the same conditions as in Example 6, and the relationship between the irradiation time until the back surface of the sample reached a pencil hardness of ``H'' and the sample thickness is shown by curve Y in the figure.

From this curve, it is clear that even with a thickness of about 4 mm (7 plies), it takes about 35 minutes to cure, which is much slower than in the case of curve X.

[Brief explanation of the drawing]

The figure shows UV irradiation of a Bripreg sheet impregnated with the ultraviolet resin composition of the present invention and a Bripreg sheet impregnated with a resin composition that does not contain glass microspheres, until the back surface of the sheet reaches a certain hardness. It is a figure showing the relationship between time and sample thickness.

Claims (1)

[Claims] 1 100 parts by weight of an ultraviolet curable resin compound and 30 to 600 parts by weight of glass microspheres with a particle size in the range of 60 to 850 μ and a single particle size distribution, or within the above particle size range 3 of glass microspheres with different particle size distributions.
An ultraviolet curable resin composition comprising 0 to 1000 parts by weight.