JPS6049648B2 - Non-foaming curable resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a non-foaming curable resin composition comprising a urethane prepolymer, a polyethylene glycol compound, a carbon dioxide absorbent, an aqueous emulsion and a dispersion aid.

Conventionally, there has been known a method of curing urethane prepolymers using inexpensive water as an active hydrogen compound as a curing agent.

This method is not preferred because carbon dioxide gas generated during the curing reaction remains in the cured product, forming a porous cured product with low mechanical strength. Although it is possible to produce non-foamed cured products by using carbon dioxide absorbents such as magnesium oxide, calcium oxide, slaked lime, and cement, the mechanical properties of the cured products are insufficient. can be,
The fundamental defect was that the curing speed was also insufficient. The object of the present invention is to solve these problems and provide a non-foaming, fast-curing resin composition with good mechanical properties.

The non-foaming curable resin composition of the present invention consists of a urethane prepolymer, a water-soluble polyethylene glycol compound, a carbon dioxide absorbent, an aqueous emulsion, and a dispersion aid, and includes a water-soluble polyethylene glycol compound with a specific molecular weight as a curing agent component. By using an aqueous emulsion, the mechanical strengths such as high elongation, tensile strength, and tear strength, which were insufficient when using only water, were significantly improved. Aqueous emulsions also serve to speed up the curing of the composition. In the composition of the present invention, the isocyanate group of the urethane prepolymer reacts with water and functional groups such as terminal or side chain hydroxyl groups and carboxyl groups of polyethylene glycol compounds and emulsion polymers, and rapidly cures while generating carbon dioxide gas. Although it forms,
A non-foamed cured product from which carbon dioxide is easily removed by the carbon dioxide absorbent is obtained.

It is believed that the dispersion aid promotes the dispersion of the carbon dioxide absorbent and allows the carbon dioxide absorbent to efficiently exert its carbon dioxide absorption ability. The water-soluble polyethylene'glycol compound used in the composition of the present invention is a compound that at least partially has a polyethylene glycol moiety and is water-soluble at room temperature, and has an average molecular weight of 1000 to 10000, preferably 20.
It is from 00 to 8000.

In practical terms, linear polyethylene glycol is most suitable. If the average molecular weight is less than 1,000, the elongation rate of the cured product will be low and other mechanical properties will also decrease. If the average molecular weight exceeds 10,000, the elongation rate of the cured product will improve, but other mechanical properties and elasticity will decrease.

The amount of polyethylene glycol to be used is 5 to 100 parts by weight, preferably 10 to 5 parts by weight, and more preferably 15 to 30 parts by weight, based on 100 parts by weight of the urethane prepolymer, but less than 5 parts by weight may cause a cured product. If the amount exceeds 100 parts by weight, the elongation rate increases but the mechanical strength decreases. The carbon dioxide absorbent used in the non-foaming curable resin composition of the present invention is a hydroxide of an alkaline earth metal such as calcium oxide or magnesium oxide, or Bortland cement containing these, which reacts with carbon dioxide gas to form carbonate. Compounds that produce and substances containing these can be used, generally in powder form.

Of these, Boltland cement is the most practical. The carbon dioxide absorbent is used in an amount of 20 to 2 (4) parts by weight, preferably 30 to 150 parts by weight, per 100 parts by weight of the urethane prepolymer, but if it is less than 20 parts by weight, the carbon dioxide absorption rate is generally insufficient. Unable to avoid foaming, 2
If the amount exceeds 0.00 parts by weight, the cured product loses its elasticity and its elongation rate decreases, so it is not suitable for the present invention. Examples of aqueous emulsions used in the non-foaming curable resin composition of the present invention include emulsions of vinyl acetate homopolymerization, vinyl acetate and (
(Meth) copolymerization with unsaturated acids such as acrylic acid, maleic acid, and fumaric acid and their esters, and copolymerization with other monomers that can be copolymerized with vinyl acetate, such as copolymerization emulsions with vinyl acetate and ethylene. Polymerization emulsion, and copolymerization of methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, etc. with methyl methacrylate, styrene, etc. (
Meth)acrylate copolymer emulsions, self-crosslinking type and reactive (meth)acrylate copolymer emulsions, styrene-butadiene copolymer latex (SBR), acrylonitrile-butadiene copolymer latex, methyl methacrylate. -Tobutadiene copolymer latex (MBR), carboxylated latex modified with various functional monomers, self-crosslinking latex, and other emulsions of various synthetic resins are typical. Aqueous emulsions usually have a solid content of 1
It is used after being adjusted to about 0 to 50% by weight, and the solid content is 1 to 20% based on 100 parts by weight of the urethane prepolymer.
Parts by weight, preferably 3 to 1 parts by weight, more preferably 5 parts by weight
~1 volume part is used. If the solid content of the aqueous emulsion is less than 1% by volume, the mechanical properties of the cured product will be poor, and if it exceeds 5% by volume, curing will tend to be difficult. Furthermore, if it is less than 1 part by weight per 100 parts by weight of the urethane prepolymer, rapid curing will not be obtained, and non-foaming will be difficult and mechanical properties will deteriorate, while if it exceeds 1 part by weight, mechanical properties such as elongation rate will deteriorate. descend. The urethane prepolymer used in the non-foamed curable resin composition of the present invention is obtained by a conventional method, and is made by combining diisocyanate or polyisocyanate with polyester polyol or polyether polyol, etc. Typical products are those manufactured by reacting at high temperatures, and the viscosity is generally 3000 to 2000 from the viewpoint of elongation rate and curing speed.
0CpS/25°C is used.

Diisocyanates used for this purpose include, for example, tetramethylene diisocyanate, tetraethylene diisocyanate, pentamethylene diisocyanate, octamethylene diisocyanate, dipropyl ether 3.3" diisocyanate, dicyclohexylmethane 4◆4" diisocyanate, 1◆4-cyclohexylene diisocyanate, xylene diisocyanate. , diphenylmethane 4.
Typical examples include 4" diisocyanate, metaphenylene diisocyanate, 2◆6 tolylene diisocyanate, 2,4 tolylene diisocyanate, etc. Polyisocyanates include, for example, 1-methylbenzoyl 2,4,6 tolylene isocyanate, naphthalene 1, Typical examples include 3.7 triisocyanate, biphenyl 2.4.4'' triisocyanate, and toluene 2.4.6 triisocyanate. Polyester polyols are obtained by conventional methods by combining dicarboxylic acids and polyols. Polyether polyols can also be prepared using conventional methods such as ethylene oxide, propylene oxide, trimethylene oxide, butylene oxide, α-methyltrimethylene oxide, 3●3″ dimethyltrimethylene oxide,
It is produced by ring-opening polymerization or copolymerization of cyclic ethers such as tetrahydrofuran, dioxane, etc. The equivalent ratio (NC
O/0H) is usually 1.5 to 3.0, and the isocyanate group contained in the urethane polymer is preferably about 2 to 15% by weight from the viewpoint of elongation rate and curing speed, and particularly 2.5
It is preferably about 8% by weight.

The average molecular weight of the polyester polyol or polyether polyol is usually 300 to 100,001, especially 10
00-7000 is preferable. As the dispersion aid used in the non-foamed curable resin composition of the present invention, various tars such as pitches such as coal tar, oil tar, process oil, liquid coal tar pitch, petroleum pitch, and wood pitch are preferred. , other aromatic plasticizers such as dioctyl phthalate, dimethyl phthalate, octyldecyl phthalate, dibutyl phthalate, dihexyl phthalate, didecyl phthalate, etc., aliphatic plasticizers such as dioctyl adipate, dioctyl sebacate, dibutyl sebacate, etc., or tricresyl Rufusphate, dibutyl epoxy stearate, dimethyl maleate, etc. can also be used.

These may be used alone or in combination of two or more. These dispersion aids are used in an amount of 1 to 2 times the weight of the carbon dioxide absorbent, preferably 113 to 1 times, more preferably 113 to 1 times by weight.
Use 1 heel amount times. If the weight of the composition is less than 114 times that of the carbon dioxide gas absorbent, it is difficult to obtain non-foaming and fast curing properties of the composition, resulting in decreased uniformity and insufficient mechanical properties. If the weight exceeds twice that of the carbon dioxide absorbent, the elongation rate and mechanical properties will decrease, making it impractical. The mixing order of the non-foaming curable resin composition of the present invention is usually that a dispersion aid and a carbon dioxide absorbent are uniformly mixed and then uniformly dispersed in a urethane prepolymer, and then this is preliminarily mixed with a polyethylene glycol compound and an aqueous emulsion. It is common to mix a homogeneous mixture of the following, but it is not necessarily limited to this.

The non-foamed resin composition of the present invention can be used for roof waterproofing, basement waterproofing, internal and external waterproofing of subway structures, undersea tunnel waterproofing, underground storage tank waterproofing, rust prevention, etc., and is particularly suitable for fields requiring quick curing. ing.

EXAMPLES Below, the present invention will be explained in more detail by showing examples together with comparative examples, but the present invention is not limited to the following examples. In the following, parts, percentages, and ratios are based on weight unless otherwise specified. Example 1 Urethane prepolymer (
Hypren P-760 manufactured by Mitsui Toatsu Chemical Co., Ltd. (isocyanate content: 7.5%), polyethylene glycol with an average molecular weight of 6000, cement as a carbon dioxide absorbent (
Voltland cement manufactured by Onoda Cement), carboxyl-modified MBR (solid content 47.5%, Mitsui Toatsu Chemical Co., Ltd.)
Product Polylac 750, methyl methacrylate butadiene copolymer) and liquid coal tar (manufactured by Yoshida Refinery, Tarclone 180L1) in the mixing ratios shown in Table 1, and in the order of addition, urethane was added to a homogeneous mixture of coal tar and cement. The prepolymer is mixed uniformly, and then a uniform mixture of carboxyl-modified MBR, polyethylene glycol, and water if necessary is mixed.

Using a stainless steel mold treated with a silicone mold release agent and a squeezing rod, this was made into approximately 300TWL x 300cm x 2? The physical properties of the sheet obtained by highly curing were measured according to JISA6O2l (roof coating waterproofing material).

In addition, the content of bubbles in the cured product is determined separately by length x width x height = 1
A cured product measuring cm×2α×5 cm was prepared, and the presence or absence of bubbles on the cut surface at a height of 112 was observed. Curability was measured by mixing at 20'C and measuring the time taken until the fluidity of the mixture stopped.
The results are shown in Table 1. Example 2 Urethane prepolymer (Hypren P-302 manufactured by Mitsui Toatsu Chemical Co., Ltd., isocyanate 3.2%), cement as a carbon dioxide absorbent (Boltland Cement manufactured by Onoda Cement), the same water-based material as in Example 1. The emulsion and the dispersion aid were mixed uniformly in the same addition order as in Example 1, with the proportions of polyethylene glycol having an average molecular weight of 8,000 being varied as shown in Table 2.

The physical properties of the cured sheet, presence/absence of bubbles, and curing properties were measured in the same manner as in Example 1. The results are shown in Table 2. Example 3 The same urethane prepolymer as in Example 1, slaked lime as a carbon dioxide absorbent, and nocarboxyl-modified SBR (solid content 50%, manufactured by Mitsui Toatsu Chemical Co., Ltd.), styrene-butadiene-based copolymer and Polymer), a mixture of coal tar (Yoshida Refinery Turclone 180U) as a dispersion aid and aromatic plasticizer dioctyl phthalate at a weight ratio of 1:1, and polyethylene glycol at a constant blending ratio, Table 3 The polyethylene glycol was uniformly mixed in the same order of addition as in Example 1, except that the average molecular weight of the polyethylene glycol was changed.

The physical properties of the cured sheet, the presence or absence of bubbles, and the curing properties were measured in the same manner as in Example 1. The results were as shown in Table 3. Example 4 Urethane prepolymer (product manufactured by Mitsui Toatsu Chemical Co., Ltd. Hypren P-8201 Isocyanate 5.5
%), polyethylene glycol with an average molecular weight of 6000,
and U-Rex #1 manufactured by Tokyo Jushi Kogyo Co., Ltd. as a dispersion aid.
70 at constant mixing ratios, cement (Boltland Cement manufactured by Onoda Cement) as a carbon dioxide absorbent and MBR (solid content 47.5%,
Polylac 501, a product manufactured by Mitsui Toatsu Chemical Co., Ltd., methyl methacrylate, butadiene copolymer) was uniformly mixed in the same addition order as in Example 1, with the mixing ratios shown in Table 4 changed.

The physical properties of the cured sheet, the presence or absence of bubbles, and the curing properties were measured in the same manner as in Example 1. The results are shown in Table 4. Example 5 The same urethane prepolymer as in Example 1, cement (Boltland Cement manufactured by Onoda Cement) as a carbon dioxide absorbent, and the same carboxyl-modified ■■ as in Example 1 and polyethylene glycol with an average molecular weight of 6000 as an aqueous emulsion in the blending proportions. is kept constant, the same coal tar as in Example 1 is used as a dispersion aid, and the mixing ratio shown in Table 5 is changed, and the mixture is uniformly mixed in the same order of addition as in Example 1.

The physical properties of the cured sheet, the presence or absence of bubbles, and the curing properties were measured in the same manner as in Example 1.

Claims (1)

[Claims] 1 100 parts by weight of urethane prepolymer, average molecular weight 1
000 to 10,000 polyethylene glycol compound, 20 to 200 parts by weight of a carbon dioxide absorbent, 1 to 20 parts by weight of an aqueous emulsion as a solid content, and a dispersion aid of 1/4 to 2 parts by weight of the carbon dioxide absorbent. A non-foaming curable resin composition containing twice the amount by weight.