JP3369218B2 - Method for producing polyurethane resin / vinyl compound-based room temperature curable resin composition - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polyurethane resin / vinyl compound-based room temperature curable resin composition which is used for flooring materials and coating materials in the field of building materials and which can be cured at room temperature for a short time.

[0002]

BACKGROUND OF THE INVENTION As a room temperature curable resin, unsaturated polyester resins used in baths, septic tanks, tanks, boats and the like are well known. These curable resins are used as fiber reinforced plastics. It is limited to the field of molded products with high hardness and low elongation.

On the other hand, since flooring and coating materials in the field of building materials are required to have appropriate flexibility, polyurethane, polyvinyl chloride, polyacrylate, etc. are used.
Polyurethane is excellent in finishing performance, but in workability, moisture curing, cross-linking curing with low molecular weight glycol, or curing with aromatic amine is adopted, but in both cases it takes one day to complete curing at room temperature. It also has a drawback that the working time is long.

As a material having improved workability, a resin composition of a soft unsaturated polyester is also found, but when it is used as a flooring material, a waterproof material, etc., the decrease in flexibility due to curing is largely caused by temperature dependence. Since it changes, there is a problem in that the groundwork during construction work needs attention.

[0005]

DISCLOSURE OF THE INVENTION The present invention provides a curable resin based on a polyurethane resin / vinyl compound, which improves the curing workability of the above-mentioned polyurethane resin system and has excellent tear strength properties and which can be cured at room temperature for a short time. It is an object to provide a method for producing a composition.

[0006]

SUMMARY OF THE INVENTION The present invention provides a polyurethane resin having improved curing workability without impairing the performance of the polyurethane resin used as a flooring material, waterproof material and coating material as a building material. The present invention relates to a method for producing a vinyl compound-based room temperature curable resin composition.

The present invention is directed to the terminal NC of urethane prepolymer.
95: 5 to 60: a polyurethane resin in which an O group is blocked with a vinyl compound having active hydrogen and a polyalkylene ether monoalcohol modified at one end and a vinyl compound.
It is a method for producing a polyurethane resin / vinyl compound-based room temperature curable resin composition, which is characterized by mixing in a weight ratio of 40 .

In the NCO-terminated urethane prepolymer, as polyisocyanate compounds, aliphatic polyisocyanates (eg, ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, etc.) and alicyclic polyisocyanates (eg, isophorone diisocyanate, dicyclohexylmethane) are used. Diisocyanate, cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, etc.) or aromatic polyisocyanate (for example, tolylene diisocyanate, diphenylmethane diisocyanate, polyphenylmethane polyisocyanate, xylylene diisocyanate, naphthylene diisocyanate, etc.) and a polyisocyanate compound selected from From That.

As the polyol of the urethane prepolymer, polyether glycol such as polyethylene ether glycol, polypropylene ether glycol, polytetramethylene ether glycol, poly (tetrahydrofuran / 3-methyltetrahydrofuran copolymer) glycol, or polycarboxylic acid (aliphatic Saturated or unsaturated polycarboxylic acids such as adipic acid, azelaic acid, dodecanoic acid, fumaric acid, maleic acid, itaconic acid,
And it is obtained by the ring-opening polymerization of polyester polyol, polyether ester polyol, or ε-caprolactone, which is obtained by the condensation reaction of phthalic acid, isophthalic acid as an aromatic polycarboxylic acid) and a low molecular weight polyol or polyether polyol. Examples thereof include polyols such as polycaprolactone polyols having an average molecular weight of 300 to 5,000, preferably 400 to 1,000.

When the NCO-terminated urethane prepolymer is obtained by using these raw materials, the NCO of polyisocyanate is used.
The molar ratio of radical to active hydrogen of the polyol is usually 1.5: 1.
0-3.5: 1.0, preferably 1.8: 1.0-2.
It is 1: 1.0. The prepolymerization reaction is usually carried out at a reaction temperature of 40 to 90 ° C, preferably 60 to 80 ° C.

As the vinyl compound represented by the following general formula (Formula 1) having active hydrogen which is a compound for reacting with the terminal NCO group of the urethane prepolymer, hydroxyl (meth) acrylate, hydroxyethyl (meth) acrylate, Examples thereof include hydroxypropyl (meth) acrylate, triethylene glycol (meth) acrylate, allyl alcohol and the like.

[Chemical 4] [In the formula (Formula 1), A is A ′ or an organic group represented by —COOA′—, and A ′ represents an alkylene group. R represents a hydrogen atom or an alkyl group. ]

As the one-end modified polyalkylene ether monoalcohol, as described in JP-A No. 63-105029, a compound containing one active hydrogen atom is allowed to coexist, and 3 or 4 capable of being polymerized with a Lewis acid. Examples thereof include those represented by the general formula (Formula 2) and the general formula (Formula 3) obtained by polymerizing tetrahydrofuran or 3-methyltetrahydrofuran on a member cyclic ether.
The molecular weight of the polyalkylene ether monoalcohol modified at one end is 300 to 5000, preferably 600 to 17.
00.

[Chemical 5] [Wherein, l represents a positive integer, m is 0 or a positive integer
Represent R'represents a C _X H _Y group, X = 1 to 10, Y = 4
~ 12. ]

[Chemical 6] [In the formula, n represents 0 or a positive integer, and p represents a positive integer.
, Q represents 0 or a positive integer, and the relationship of n + p> q
Have. R'represents a C _X H _Y group, X = 1 to 10, Y
= 4-12. R ′ in the general formulas (Formula 2) and (Formula 3) is composed of a saturated component of an aliphatic alcohol and an unsaturated alcohol represented by a C _X H _Y group, and a residue component of an aromatic alcohol. Especially preferred are the residual components of saturated aliphatic alcohols and aromatic alcohols.

As a method for reacting the NCO-terminated prepolymer with the one-end modified polyalkylene ether monoalcohol and the vinyl compound having active hydrogen, 3 to 9 is used.
% Of urethane prepolymers with terminal NCO groups of 0.
1 to 140% by weight of one-end modified polyalkylene monoalcohol required to consume 1 to 5%, preferably 0.5 to 2% of terminal NCO groups is reacted at 60 to 90 ° C., and after reaction for a certain period of time. The residual NCO group of the urethane prepolymer partially modified at the end is analyzed, and a vinyl compound having active hydrogen sufficient to consume the remaining NCO group is added, and the reaction temperature is 20 to 700 ° C., preferably 50 to The reaction is carried out at 60 ° C. to obtain a curable polyurethane resin.

This polyurethane resin is a viscous liquid,
It is used in the form of being dissolved in a vinyl compound. The vinyl compound used here is styrene, vinyltoluene, divinylbenzene, or mono- or diesters of (meth) acrylic acid.

The mixing ratio of the vinyl compound and the curable polyurethane resin is not particularly limited and is mainly determined from the viewpoint of workability, but usually 10 parts by weight of the vinyl compound to 100 parts by weight of the curable polyurethane resin. Appropriately not less than 100 parts by weight and not more than 100 parts by weight, and the best ratio is 20 to 50 parts by weight. If necessary, the mixture of the curable polyurethane resin / vinyl compound may contain magnesium hydroxide, aluminum hydroxide, calcium carbonate,
Filler such as talc, zinc oxide, titanium white, glass fiber,
A reinforcing material such as carbon fiber or a coloring material can be added.
Further, it can be used in combination with other unsaturated polyester resin or the like.

As a curing method for these room temperature curable polyurethane resin / vinyl compound type curable resin compositions, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide and methyl ethyl ketone, which are general curing catalysts for unsaturated polyesters, are used. Organic peroxides such as peroxide, cyclohexanone peroxide, t-butyl hydroperoxide, cumene hydroperoxide, ditertiary butyl peroxide and dicumyl peroxide are used.

As a curing catalyst accelerator, diphenyl sulfite, quaternary ammonium salt, β-diketones, cobalt naphthenate, cobalt acetylacetonate, dimethylaniline, triethanolamine, N, N.
-Dimethylaniline, phenylphosphinic acid and the like are used.

[0018]

The contents of the present invention will be described in detail with reference to the following examples. [Example-1] Polypropylene ether glycol having a molecular weight of 710 (Exenol 720 manufactured by Asahi Glass Co., Ltd.), 100 g (0.
140 mol) and 2,4-toluene diisocyanate (T-100 manufactured by Nippon Polyurethane Industry Co., Ltd.) 45.
6 g (0.261 mol) are mixed and, with stirring, 80-85
The reaction is carried out at 2.5 ° C. for 2.5 hours, and ethyl polytetramethylene ether monoalcohol with one terminal (molecular weight 166
0) 19.2 g was added, the reaction at 80 to 85 ° C. for 2.5 hours was continued, and then the NCO analysis of the terminal of the urethane prepolymer was performed, and it was 6.2%. To this urethane prepolymer, 32 g of 2-hydroxyethyl methacrylate
(0.246 mol) was added and the reaction was carried out at 55-60 ° C. for 4 hours to obtain a colorless and transparent viscous liquid substance. The NCO group content of this curable polyurethane resin was zero.

Example 2 Polypropylene ether glycol having a molecular weight of 710 (Exenol 720 manufactured by Asahi Glass Co., Ltd.) 100 g (0.1
40 mol) and 4,4-toluene diisocyanate (T-100 manufactured by Nippon Polyurethane Industry Co., Ltd.) 45.6 g
(0.261 mol) were mixed and reacted for 2.5 hours at 80 to 85 ° C. under stirring, and 18.7 g of ethyl poly (tetramethylene / 3-methyltetramethylene ether) monoalcohol (molecular weight 1400) at one end thereof was added thereto. And add 8
After continuing the reaction for 2.5 hours at 0 to 85 ° C., the terminal NCO analysis of the urethane prepolymer was 6.1%. To this urethane prepolymer, 30.8 g (0.237 mol) of 2-hydroxyethyl methacrylate was added and the reaction was carried out at 55-60 ° C. for 4 hours to obtain a colorless and transparent viscous liquid. NC of this curable polyurethane resin
The O group content was 0.

Example 3 100 g (0.103) of poly (tetramethylene / 3-methyltetramethylene ether) glycol having a molecular weight of 965
Mol) and 2,4-toluene diisocyanate (T-100 manufactured by Nippon Polyurethane Industry Co., Ltd.) 38.0 g
(0.218 mol) are mixed, 2.5 hr reaction is carried out at 80 to 85 ° C. under stirring, 19.0 g of ethyl polytetramethylene ether monoalcohol (molecular weight 1660) at one end is added thereto, and 80 to 85 ° C. After continuing the reaction for 2.5 hours, the NCO analysis of the urethane prepolymer was 5.8%. To this urethane prepolymer, 2-hydroxyethyl methacrylate, 29.0 g
(0.223 mol) was added and the reaction was carried out at 55-60 ° C. for 4 hours to obtain a colorless and transparent viscous liquid substance. The NCO content of this curable polyurethane resin was zero.

Example 4 100 g (0.1 mol) of polytetramethylene ether glycol having a molecular weight of 1000 and 2,4-toluene diisocyanate (T-10 manufactured by Nippon Polyurethane Industry Co., Ltd.)
0) and 38 g (0.218 mol) were mixed and stirred under stirring 80
After carrying out 2.5 hr reaction at ˜85 ° C., 20 g of ethyl poly (tetramethylene / 3-methyltetramethylene ether) monoalcohol (molecular weight 1650) at one end was added thereto, and after the reaction was continued, the end NC of the urethane prepolymer was terminated.
O analysis revealed 6.0%. To this urethane prepolymer, 30.0 g (0.230 mol) of 2-hydroxyethyl methacrylate was added and the reaction was carried out at 55-60 ° C. for 4 hours to obtain a colorless and transparent viscous liquid. The NCO group content of this curable polyurethane resin was zero.

Comparative Example-1 Polypropylene ether glycol having a molecular weight of 710 (Exenol 720 manufactured by Asahi Glass Co., Ltd.), 100 g (0.
140 mol) and 2,4-toluene diisocyanate (T-100 manufactured by Nippon Polyurethane Industry Co., Ltd.) 42.
Mix 9 g (0.246 mol) and, with stirring, 80-85
The reaction was performed at 2.5 ° C. for 2.5 hours, and the NCO analysis of the obtained urethane prepolymer was 6.3%. To this urethane prepolymer, 28.2 g (0.217 mol) of 2-hydroxyethyl methacrylate was added and the reaction was carried out for 4 hours at 55 to 60 ° C., which had a colorless and transparent viscous liquid and was blocked with 2-hydroxyethyl methacrylate at both ends. A curable polyurethane resin was obtained.

[Comparative Example 2] A polypropylene ether glycol having a molecular weight of 2000 was used to carry out the same reaction as in Comparative Example 1 with both ends being 2-
A curable polyurethane resin consisting of hydroxyethyl methacrylate, 6.0% was obtained.

[Comparative Example 3] Using polytetramethylene ether glycol having a molecular weight of 1000, the same reaction as in Comparative Example 1 was carried out, and curing was performed with 2-hydroxyethyl methacrylate at both ends of 6.0%. A possible polyurethane resin was obtained.

[Examples 1 to 4] and [Comparative Example 1]
To 3], the curable polyurethane resin is mixed with a copolymerizable vinyl compound, an organic peroxide and a curing accelerator are added, and the cured product performance when cured at room temperature for a short time is The results are shown in [Table 1]. It can be seen that a cured product excellent in tensile strength and tear strength can be obtained as compared with the comparative example.

[0026]

[Table 1]

[0027]

EFFECTS OF THE INVENTION By introducing a polyalkylene ether monoalcohol modified at one end into a polyurethane resin / vinyl compound system room temperature curable resin composition, a viscous liquid is obtained.
The curing speed was increased compared to the curing method using polyol crosslinking or the like. It was possible to provide a polyurethane resin / vinyl compound-based room temperature curable resin composition in which the flexibility of the urethane elastomer is not impaired and the tear strength is improved.

Claims (10)

(57) [Claims] 1. A polyurethane resin in which a terminal NCO group of a urethane prepolymer is capped with a vinyl compound having active hydrogen and a polyalkylene ether monoalcohol modified at one end and a vinyl compound at 95: 5 to 60:40.
A method for producing a polyurethane resin / vinyl compound-based room temperature curable resin composition, which is characterized by being mixed in a weight ratio of 1. 2. The polyurethane resin / vinyl compound-based room temperature curable resin composition described above contains one kind or two or more kinds selected from a filler, a reinforcing material, and a coloring material. A method for producing the polyurethane resin / vinyl compound-based room temperature curable resin composition as described. 3. The urethane prepolymer comprises a diisocyanate compound and a polyol having a molecular weight of 400 to 1000 in a molar ratio of NCO groups to active hydrogen groups of 1.5: 1 to 3.
3. The method for producing a polyurethane resin / vinyl compound-based room temperature curable resin composition according to claim 1, which is obtained by mixing and reacting in a range of 5: 1. 4. The polyol having a molecular weight of 400 to 1000, which is a raw material of the urethane prepolymer, is polytetramethylene ether glycol or poly (tetrahydrofuran / 3-methyltetrahydrofuran copolymer) glycol. 3. The method for producing a polyurethane resin / vinyl compound-based room temperature curable resin composition according to any one of 3 above. 5. The terminal N of the urethane prepolymer described above.
CO group, vinyl compounds and one terminal-modified polyalkylene ether monoalcohol blocked polyurethane resin having active hydrogen, according to any of claims 1 to claim 4, characterized in that the viscous liquid 1. A method for producing a room temperature curable resin composition of polyurethane resin / vinyl compound. 6. The terminal N of the urethane prepolymer described above.
The above-mentioned vinyl compound having active hydrogen is reacted with the CO group to give a partially end-modified urethane prepolymer, and the residual NCO group of this partially end-modified urethane prepolymer is analyzed. 6. The NCO group is blocked by mixing and reacting the one-end modified polyalkylene ether monoalcohol in an amount corresponding to more active hydrogen groups or more . The method for producing a polyurethane resin / vinyl compound-based room temperature curable resin composition according to the item 1. 7. The terminal N of the urethane prepolymer described above.
The above-mentioned one-end modified polyalkylene ether monoalcohol is reacted with the CO group to give a partially end-modified urethane prepolymer, and the residual NCO group of this partially end-modified urethane prepolymer is analyzed to determine the residual NCO group. 6. A vinyl compound having the above-mentioned active hydrogen in an amount equivalent to or more than the equivalent amount of the active hydrogen group is mixed and reacted to block the NCO group . The method for producing a polyurethane resin / vinyl compound-based room temperature curable resin composition according to the item 1. 8. The terminal N of the urethane prepolymer described above.
The above-mentioned vinyl compound having active hydrogen to be reacted with a CO group has a structure represented by the general formula (Formula 1),
10-35 to 100 parts by weight of urethane prepolymer
Method for producing a mixture of parts by weight, the polyurethane resin / vinyl compound cold-curable resin composition according to any one of claims 1 to claim 7 is to react. [Chemical 1] [In the formula, A is a divalent organic group represented by A'or -COOA'-, and A'represents an alkylene group. R represents a hydrogen atom or an alkyl group. ] 9. The terminal N of the urethane prepolymer described above.
The one-end modified polyalkylene ether monoalcohol to be reacted with the CO group is a one-end modified polyalkylene ether monoalcohol having a molecular weight of 600 to 1700 represented by the general formula (Formula 2) or the general formula (Formula 3), 2 to 100 parts by weight of urethane prepolymer
The method for producing a polyurethane resin / vinyl compound-based room temperature curable resin composition according to any one of claims 1 to 8 , wherein 50 parts by weight are mixed and reacted. [Chemical 2] [Wherein, l represents a positive integer, m is 0 or a positive integer
Represent R'represents a C _X H _Y group, X = 1 to 10, Y = 4
~ 12. ] [Chemical 3] [In the formula, n represents 0 or a positive integer, and p represents a positive integer.
, Q represents 0 or a positive integer, and the relationship of n + p> q
Have. R'represents a C _X H _Y group, X = 1 to 10, Y
= 4-12. ] 10. The one-end modified polyalkylene ether monoalcohol represented by the above general formula (Formula 3) is used as a polyalkylene ether component of poly (tetrahydrofuran / 3-methyltetrahydrofuran copolymer).
Any of claims 1 to 9 containing a glycol.
The method for producing a polyurethane resin / vinyl compound-based room temperature curable resin composition according to any one of the items.