JPH107901A - Urethane resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a waterproofing material which is applied to the roof of a building, has good weatherability and excellent discoloration resistance, reduces the burden on the maintenance, and enables a shortened initial construction period. SOLUTION: This composition comprises poly[ 6-(1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} 2,2,6,6,-tetramethyl-4-piperidyl) imino}hexamethylene (2,2,6,6-tetramethyl-4-piperidyl)imino}] and bis(1,2,2,6,6- pentamethyl-4-piperidyl) sebacate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a waterproof material to be installed on the roof of a building which has good weather resistance, reduces the burden of maintenance, and can shorten the construction period at the time of construction.

[0002]

2. Description of the Related Art Generally, a resin material is laid on the roof of a building for waterproofing, and a urethane resin composition is widely used as the waterproofing resin material. It is desirable that the material has sufficient weather resistance because it is exposed to direct sunlight, but none of the conventional products have sufficient weather resistance, and the deterioration of the material proceeds rapidly, and waterproofing is performed in a few years. It will hinder performance. For this reason, on the resin material for waterproofing,
It is widely practiced to apply a material generally called "top coat" to improve weather resistance. This extends the weathering retention period to approximately 5-6 years. However, since the top coat is applied after the first-layer waterproofing material is almost dried, the construction time is prolonged when the top coat is applied. However, even if a top coat is applied, the weather resistance retention period can be extended only for about three years, so it has sufficient weather resistance by itself, requires no top coat, requires a short construction period, and has high weather resistance. A waterproof material that does not require maintenance is desired. Conventionally, nickel dibutyl dithiocarbamate (NBC) has been widely used as a stabilizer blended in a urethane resin-based waterproofing material.
BC has a problem that it does not have sufficient weather resistance and yellows in a short period of time after construction.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems. The present invention has good weather resistance, so that the burden of maintenance can be reduced, the discoloration resistance is excellent, and the initial construction period can be shortened. Provide waterproofing material to be installed on the roof of a building.

[0004]

Means for Solving the Problems After diligent research, the present inventors have found that remarkable weather resistance can be exhibited by using two specific hindered amine stabilizers in combination with a urethane resin composition. Completed the study. That is,
An object of the present invention is to provide poly [{6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,
4-diyl} (2,2,6,6-tetramethyl-4-
Piperidyl) imino {hexamethylene} (2,2,6)
6-tetramethyl-4-piperidyl) imino}] (A)
And bis (1,2,2,6,6, -pentamethyl-
Provided is a urethane resin composition containing (4-piperidyl) sebacate (B).

The urethane resin composition of the present invention is a two-pack type urethane resin composition obtained by reacting a main agent and a curing agent in consideration of storage stability, curing speed, and the ability to arbitrarily select the thickness of a coating film. It is preferred that

[0006] The two-pack type urethane resin composition comprises a main agent comprising an isocyanate compound and a curing agent mainly comprising a crosslinking agent, a filler, a pigment and the like.

The isocyanate compound used in the present invention is not particularly limited as long as it contains an isocyanate group at a molecular terminal, and may be a polyisocyanate compound used in a usual polyurethane resin composition, or may be an excess of a polyol compound. And a reaction product obtained by reacting the above polyisocyanate compound, and may be a so-called urethane prepolymer containing an isocyanate group at a molecular terminal.

[0008] Polyisocyanate used in the present invention
As a compound, it is used in ordinary polyurethane resin compositions.
There are various examples, and specifically,
Diisocyanate (2,4-TDI), 2,6-tri
Range isocyanate (2,6-TDI), 4,4'-
Diphenylmethane diisocyanate (4,4'-MD
I), 2,4'-diphenylmethane diisocyanate
(2,4'-MDI), p-phenylene diisocyanate
G, polymethylene polyphenylene polyisocyanate,
Xylylene diisocyanate (XDI), 1,5-naph
Aromatic polyiso such as talendiisocyanate (NDI)
Cyanate; hexamethylene diisocyanate (HD
Aliphatic polyisocyanates such as I); isophorone diiso
Cyanate, H ₆XDI (hydrogenated XDI), H₁₂MDI
Alicyclic polyisocyanates such as (hydrogenated MDI);
Carbodiimide-modified polyisocyanate of polyisocyanate
, Or their isocyanurate-modified polyisomers
Cyanate and the like. One or more of these
Used as a combination above.

The urethane prepolymer used in the present invention is not particularly limited as long as it is formed from a polyisocyanate compound and a polyol used in a general polyurethane resin composition. Can use the above-mentioned polyisocyanate compound.

On the other hand, the polyol used in the present invention includes polyether polyols, polyester polyols, other polyols, and mixed polyols thereof as in the preparation of ordinary urethane prepolymers. Specifically, examples of the polyether polyol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 4,4′-dihydroxyphenylpropane, and 4,4 ′. Dihydric alcohols such as dihydroxyphenylmethane; glycerin,
Polyhydric alcohols such as 1,1-trimethylolpropane, 1,2,5-hexanetriol and pentaerythritol; diamines such as ethylenediamine and aromatic diamine; saccharides such as sorbitol; Polyols obtained by adding one or more alkylene oxides such as oxide, propylene oxide, butylene oxide and styrene oxide; and polyoxytetramethylene oxide.

The polyester polyols are broadly classified into condensed polyester polyols, lactone polyols, and polycarbonate diols. Specifically, ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, cyclohexanedimethanol, glycerin , 1,1,1-trimethylolpropane, or one or more other low molecular polyols, and glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, terephthalic acid, isophthalic acid, dimer acid, Alternatively, condensed polymers with one or more other low molecular carboxylic acids or oligomeric acids; ring-opened polymers such as propionlactone, valerolactone, and the like;

Further, as other polyols, polyols having a main chain composed of carbon-carbon bonds, for example, acrylic polyols, polybutadiene polyols, hydrogenated polybutadiene polyols, etc., ethylene glycol, diethylene glycol, propylene glycol,
Low molecular polyols such as dipropylene glycol, butanediol, pentanediol and hexanediol are also preferably exemplified. These polyols may be used alone or in combination of two or more.

When producing a urethane prepolymer having a terminal isocyanate group, the ratio of the amount of the polyisocyanate compound to the amount of the polyol is such that the number of hydroxyl groups in the polyol is one or less per isocyanate group in the polyisocyanate compound. But preferably 0.95
~ 0.5. The production conditions for the urethane prepolymer may be the ordinary production conditions for the urethane prepolymer. That is, the above-mentioned polyisocyanate compound and polyol may be reacted at a reaction temperature of about 50 to 100 ° C. under normal pressure.

The isocyanate compound used in the present invention may have an isocyanate group at a molecular terminal.
Although not limited to the above compounds, a prepolymer comprising polypropylene polyol (PPG) and tolylene diisocyanate (TDI) is preferable. This is because it is preferable that the waterproof material can be provided at a low cost because the construction area of the waterproof material is large.

The curing agent for the urethane resin composition of the present invention includes a crosslinking agent, a filler, a curing catalyst (curing accelerator), and, if necessary, various additives which are added to a known urethane composition. Specifically, a plasticizer, an antioxidant, an ultraviolet absorber, a coloring agent such as a pigment or a dye, a stabilizer, and the like may be added.

[0016] As the crosslinking agent, 3,3'-dichloro-
Examples include 4,4'-diaminodiphenylmethane (MOCA), polypropylene glycol (PPG), ethylene glycol, 1,4-butanediol, hydroquinone diethylol ether (BHEB) and the like.
More than one species is used. 5 to 20 parts by weight of PPG, preferably 8 to 1 part by weight per 100 parts by weight of the urethane prepolymer
An embodiment in which 5 parts by weight and 1 to 10 parts by weight, preferably 4 to 8 parts by weight of MOCA are blended is suitably exemplified. This is because the pot life can be easily secured and the effect time can be easily adjusted.

Examples of the filler include titanium dioxide, carbon black, silicic acid derivatives, talc, metal powder, calcium carbonate, clay and the like. The amount is 35 to 65 parts by weight, preferably 40 to 50 parts by weight, based on 100 parts by weight of the urethane prepolymer. This facilitates adjustment of viscosity and other physical properties.

Examples of the catalyst include metal catalysts such as dibutyltin dilaurate, dioctyltin laurate, zinc octylate, and organic bismuth compounds, and amine catalysts such as triethylenediamine morpholine amine.

As the plasticizer, benzoic acid, phthalic acid, dioctyl phthalate, trimellitic acid, pyromellitic acid,
Derivatives such as adipic acid, sebacic acid, fumaric acid, maleic acid, itaconic acid, citric acid, polyester,
Examples thereof include polyether and epoxy type. The amount is 10 to 10 parts by weight of the urethane prepolymer.
30 parts by weight, preferably 15 to 25 parts by weight. This is for adjusting viscosity and physical properties.

The composition of the present invention further comprises two specific hindered amines to enhance the stability. As the two kinds of hindered amines, poly [｛6-
(1,1,3,3-tetramethylbutyl) amino-1,
3,5-triazine-2,4-diyl {(2,2,
6,6-tetramethyl-4-piperidyl) imino {hexamethylene} (2,2,6,6-tetramethyl-4-piperidyl) imino}] (A) and bis (1,2,2,
6,6, -Pentamethyl-4-piperidyl) sebacate (B) is used. Compound (A) has the trade name CHIMAS
SORB 944FL, CHIMASSORB 944
It is commercially available as LD, and compound (B) is trade name SA
It is commercially available as NOL LS765. There is no example of a urethane resin composition in which two conventional hindered amine stabilizers are used in combination, and the present inventors clearly show that the weather resistance is specifically improved only when the above hindered amines A and B are combined. became. In particular, poly [｛6-
(1,1,3,3-tetramethylbutyl) amino-1,
3,5-triazine-2,4-diyl {(2,2,
6,6-Tetramethyl-4-piperidyl) imino {hexamethylene} (2,2,6,6-tetramethyl-4-piperidyl) imino}] (A) has a secondary amine and isocyanate Did not normally be used for urethane resins.

The amount ratio of A and B to be blended is A (parts by weight) / B
(Parts by weight) = 3/5 to 6/2, preferably 5/5 to 6/6
/ 4. The total amount of A and B added is 0.1 to 5% by weight, preferably 0.5 to 1.5% by weight, particularly preferably 0.8 to 1.2% by weight of the total weight of the composition. It is.
This is because adding a stabilizer in this range is most effective for improving weather resistance.

The present invention has found that the weather resistance of the urethane resin composition is significantly improved by adding two specific hindered amines as a stabilizer.
It is completed. Conventionally, nickel dibutyldithiocarbamate (NBC) has been widely used for imparting weather resistance to a urethane resin composition, but has the drawback that weather resistance is not sufficient and discoloration occurs in a short time. In contrast, the two types of hindered amines used in the present invention not only have excellent weather resistance but also do not discolor. Furthermore, according to the present invention, despite the drastic improvement in the weather resistance of the urethane resin composition, the conventional waterproof material construction equipment can be used as it is, and there is almost no effect on cost.

The composition of the present invention is suitable for being applied as a waterproof material to the roof of a building. By using the present invention as a waterproof material, it is no longer necessary to use a "top coat" which has been conventionally used to supplement weather resistance, thereby shortening the construction period at the time of construction and maintaining it for more than 5 years without maintenance. , Preferably having a durability of 7 to 10 years.

The method for preparing the urethane composition of the present invention is not particularly limited, and may be the same as a usual urethane composition. For example, knead the prepolymer and the crosslinking agent sufficiently at the construction site,
A method of uniformly dispersing is exemplified.

The urethane resin composition of the present invention may be of a one-component moisture-curing type which is cured by atmospheric moisture.
In this case, the components to be blended are the same as in the two-pack type except for the crosslinking agent.

The urethane resin composition of the present invention may be subjected to various changes and improvements as long as the properties of the composition of the present invention are not impaired.

[0027]

The present invention will be described in more detail with reference to the following examples. Note that the present invention is not limited to the following embodiments. (Synthesis of urethane prepolymer) Number average molecular weight 3,000
To 850 g of polypropylene glycol 0, 148 g of tolylene diisocyanate was added, and the mixture was heated at 80 ° C. for 12 hours.
By stirring and reacting, a urethane prepolymer containing 3.6% of isocyanate groups was synthesized.

A curing agent was added to the urethane prepolymer synthesized as described above in the composition shown in Table 1 and kneaded to produce various urethane resin compositions.

[0029] * Uses lead octylate and octylic acid as curing catalysts. * The numbers in the table indicate parts by weight.

As shown in Table 2, various kinds of urethane resin compositions shown in Table 2 were obtained by changing various kinds and mixing ratios of the stabilizer in the curing agent. The obtained urethane resin compositions were subjected to an accelerated exposure test using a sunshine weatherometer (conditions: black panel temperature: 63 ° C., 1 cycle: 120 minutes (spray cycle: 18 minutes)) in accordance with JIS A6008, and weather resistance and discoloration were performed. The situation was evaluated. The results are shown in Table 2. Weather resistance: The time until cracking was evaluated by visual observation. Discoloration: The degree of yellowing in the early stage (50 hours) after construction was visually evaluated. ○ No discoloration. X Discolored yellow.

[0031]

[Table 1] * The compounding amount of the stabilizer indicates parts by weight.

The stabilizers in Table 2 are as follows. NBC: Nickel dibutyl dithiocarbamate manufactured by Ouchi Shinko Chemical Co., Ltd. LS-944LD: Ciba Geigy's poly [$ 6-
(1,1,3,3-tetramethylbutyl) amino-1,
3,5-triazine-2,4-diyl {(2,2,
6,6-tetramethyl-4-piperidyl) imino {hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}] (CHIMASSORB 944)
LD). LS-765: Screw (1, 2, 2, 2) manufactured by Ciba Geigy
6,6, -Pentamethyl-4-piperidyl) sebacate (SANOL LS765).

As shown in Table 1, cracks did not occur in Examples 1 and 4 for 3000 hours for Examples 1 and 4000 hours for Examples 2 and 3, and the weather resistance was improved. Also, NB
Unlike when C was used, no yellowing was observed.

[0034]

According to the present invention, it has good weather resistance, can reduce the burden of maintenance, has excellent resistance to discoloration, and can be installed on the roof of a building capable of shortening the initial construction period. It becomes possible to provide a waterproof material.

Claims (1)

[Claims] 1. A. Poly [{6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-
2,4-diyl {(2,2,6,6-tetramethyl-
4-piperidyl) imino {hexamethylene} (2,2
6,6-tetramethyl-4-piperidyl) imino}] and B.I. Bis (1,2,2,6,6-pentamethyl-4-
A urethane resin composition containing (piperidyl) sebacate.