JPS61275350A - Molding urethane resin composition - Google Patents

Abstract

PURPOSE:To provide the title compsn. which has excellent weather resistance and gives high-quality moldings, causes neither reduction in thickness and surface smoothness, nor discoloration, blooming and whitening and is non-tack, consisting of a polyurethane resin, an ultraviolet light absorber and a deterioration inhibitor. CONSTITUTION:An aliph. isocyanate (e.g. hexamethylene diisocyanate) contg. no unsaturated bond other than the isocyanate group is reacted with a polyester polyol to obtain a urethane resin (A) having a weight-average MW of 70,000-200,000. 20-80wt% ultraviolet absorber having an MW of 320 or above, represented by formula I (wherein R1, R2 are each a 2-12C straight-chain or branched alkyl, cycloalkyl, aryl, aralkyl) is mixed with 80-20wt% deterioration inhibitor having a weight-average MW of 2,500 or above and contg. a repeating unit of formula II (wherein R3-R6 are each H, a 1-3C alkyl; X is succinyl, glutaryl, adipoyl; n is 2-4) to obtain a modifier (B). At least 0.45pts.wt. compo nent B is blended with 100pts.wt. component A.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a specific urethane resin composition modified with a specific modifier, and a method for forming a molded article such as a film-sheet using the composition. When exposed to the outdoors for a long time, the desired thickness and surface smoothness of the molded article are maintained due to the excellent weather resistance exhibited by the composition, and discoloration, blooming, and whitening are prevented. The present invention also relates to a urethane resin composition for molding that provides a high-quality molded product that does not cause stickiness or the like.

More specifically, urethane resin A having a specific chemical composition
This relates to a urethane resin composition for molding, which contains a specific amount of a specific ultraviolet absorber component B and a specific deterioration inhibitor component C as modifiers, and that the urethane resin composition for molding is When molding into film sheets, 7 ohms, etc. for coating materials, covering materials, laminated materials, synthetic leather, fibers, etc., using various molding methods such as extrusion, calendaring, casting, and lamination. The present invention relates to a urethane resin composition for molding that exhibits especially the ability to prevent thickness reduction of molded objects, which is due to the significantly superior weather resistance that has not been achieved previously.

[Conventional technology]

Conventionally, urethane resin molded bodies have excellent mechanical properties such as impact resistance and abrasion resistance, and chemical resistance to water, oil, etc., and have been used in a wide range of applications such as building materials and automobile parts. However, urethane resin moldings generally have poor weather resistance, so when used outdoors, it is necessary to add pigments to give them a deep color, and there are significant restrictions on using them as they are. .

For example, if you use it as it is in a transparent state, etc., for a short period of time (
For example, if used outdoors (within one year), discoloration or discoloration may occur.
The surface of the molded product may become sticky, or undesirable changes such as blooming or whitening of the urethane resin component may occur.

In particular, urethane resins whose main components are boiled aliphatic isocyanates, such as hexamethylene diisocyanate and 4゜4-dicyclohexylmethane diisocyanate, which have no unsaturated bonds other than isocyanate groups, and polyester-type polyols, such as adipic acid-based polyester polyols. (Hereinafter, it may be abbreviated as A-component resin.) Molded products such as films and sheets that can be formed from this resin have a fatal disadvantage of a significant thickness reduction that is characteristic of long-term outdoor exposure. There is.

Many methods have been proposed for improving the weather resistance of urethane resins having the above-mentioned drawbacks by modifying them with specific stabilizers and the like. However, none of these methods are yet satisfactory from a practical standpoint.

For example, in Japanese Patent Publication No. 56-17386, "Production method of polyurethane sheet with improved properties", specifically, 2
-(2-hydroxy-5-methyl-phenyl)penztriazole [Tinuvin P (manufactured by Ciba Geigy)] and 2-
At least one compound represented by formula (1) such as (2-hydroxy-3-5'-diisoamyl-phenyl)benylcitriazole [Tinuvin 328 (manufactured by Ciba Geigy)] and 4-benzoyloxy-2, A polyurethane resin solution containing at least one compound represented by formula (2) such as 2,6,6-tetramethylpiperidine [Sanol LS744 (manufactured by Sankyo Co., Ltd.)] is applied onto a substrate, and then a solvent for the solution is applied. A method for producing a polyurethane sheet with excellent light resistance and gas coloring resistance has been proposed, which comprises solidifying the polyurethane sheet in a solvent solution which is compatible with the polyurethane resin but is not compatible with the polyurethane resin.

However, in the above proposal, the total amount of the compound of formula (1) and the compound of formula (2) is added to 100 parts by weight of the polyurethane resin in a relatively large amount (for example, 2 parts by weight of the film).
Even if the amount is 3.5 parts by weight (00μ), the effect of preventing thickness reduction is insufficient, and this phenomenon is particularly noticeable in the above-mentioned component A resin. In this case, it also shows a tendency to whiten. On the other hand, when using a small amount (for example, 0.5 parts by weight for a film thickness of 500μ), the expected properties of preventing discoloration, discoloration, and thickness reduction based on the expected excellent northern weather resistance cannot be obtained, and the above-mentioned performance against urethane resins still remains. There has been a strong demand for further improvement (for example, weather resistance for at least two years when used outdoors).

[Problem that the invention seeks to solve]

The present inventors have conducted extensive research into improving the weather resistance of urethane resins, which has been desired for some time. As a result, it was found that molded products such as films and sheets molded from conventional molding urethane resin compositions that use component A resin have problems with thickness reduction due to poor weather resistance. .

The present inventors have developed a special urethane resin in order to provide a high degree of weather resistance (for example, about 3 years when used outdoors) without interfering with the excellent mechanical performance and chemical resistance that urethane resin has. Further research on KA component resins was continued.

As a result, with respect to the A component resin; , Mw) and has a specific structure (hereinafter referred to as C).
Sometimes abbreviated as component. ) is within a specific weight % range; and the total weight part of the B component and the C component is at least a specific amount: When using a urethane resin composition that satisfies the various conditions, the B component The present invention was completed based on the unexpected discovery that the MC component and the MC component act synergistically on the A-component resin, thereby solving all the problems of the A-component resin described above at once.

That is, the present invention exhibits a high degree of weather resistance, maintains the initial predetermined thickness and surface smoothness of the molded product even after long-term outdoor exposure, and prevents discoloration, pluming, whitening, and adhesion. The present invention provides a molding urethane resin composition containing an aliphatic isocyanate and a polyester polyol, which has no unsaturated bonds other than an inquanate group, and which gives a high-quality molded product free from the generation of viscosity.

The above objects and other objects and advantages of the present invention will become clearer from the following description. On the other hand, the ratio of parts by weight of the ultraviolet absorber B component and the deterioration inhibitor C component is 20:80 to 80:20, and the total weight part of the B component and the C component is 0.45 parts by weight or more. This is a urethane resin composition for molding characterized by containing the following.

A. A urethane resin whose main components are an aliphatic isocyanate having no unsaturated bonds other than inquanate groups, and a polyester polyol.

80 After a molecular weight of 350 or more represented by the following general formula (in the formula: R3 or R1 may be the same or different; each has 2 to 12 carbon atoms, an optionally branched alkyl group, cycloalkyl A deterioration inhibitor having a weight average molecular weight of 2,500 or more and containing a structural unit represented by the following general formula in the C0 repeating unit.

(In the formula; R3, R1, R3 and R6 may be the same or different, each being a hydrogen atom or having 1 to 3 carbon atoms)
represents an alkyl group; X represents a succinyl group, a glutaryl group, or an adipoyl group; n represents an integer of 2 to 4; ) The aliphatic isocyanate having no unsaturated bond other than the isocyanate group, which is the raw material compound of the A component resin used in the present invention, is P-phenyl diisocyanate; 4.
So-called aromatic polyisocyanates such as 4-diphenylmethane diisocyanate, 2.4-) silane diisocyanate, 2.6-) silane diisocyanate, xylylene diisocyanate, triisocyanate, naphthalene 1,5-diisocyanate; lysine diisocyanate,
This excludes so-called aliphatic isocyanates having an unsaturated bond such as a double bond in addition to the isocyanate group, such as diethyl fumarate dioxanate. Examples of aliphatic inquanates having no unsaturated bond other than the isocyanate group include pentamethylene diicanate, hexamethylene diicanate, heptamethylene diisocyanate), 4,4-di7chlorohexylmethane diisocyanate) , 4.4-dicyclohexyldimethylmethane diisocyanate, water-added 2.4-) cyylene diisocyanate, water-added 2.6-) cyylene diisocyanate, among others, hexamethylene diisocyanate, 4-dicyclohexyldimethylmethane diisocyanate, etc. .4-Dicyclohexylmethane diisocyanate is preferred.

Polyol refers to the polyester which is another raw material compound of the A-component resin used in the present invention; polyol is a dicarboxylic acid condensed with an excessive amount of a polyol component to form a hydroxyl group at the end;
It includes polycarbonate esters having a hydroxyl group at the end, polymerized lactone glycol esters, and those condensed with castor oil.The dicarboxylic acids mentioned here include succinic acid, geltaric acid, adipic acid, pimelic acid, and superric acid. , saturated fatty acids such as azelaic acid and sebacic acid, unsaturated acids such as maleic acid and fumaric acid, aromatic acids such as phthalic acid and inktaric acid, and dimer acids. Diols such as pyrene gelicol, triethylene glycol, butylene glycol, hexamethylene glycol, glycerin, trimethylolpropane, 1,2.6-
Refers to triols such as hexanetriol and trimethylolethane, and hexaols such as pentaerythritol and sorbitol; polycarbonate esters having a hydroxyl group at the end include diethyl carbonate, A carbonate ester such as dipropyl carbonate, phenyl carbonate, etc., and a polyol as described herein are transesterified.

Among these; adipic acid, sepatic acid, maleic acid, dimeric dicarboxylic acids; polyols of ethylene glycol, diethylene glycol, propylene gellicol, butylene glycol, trimethylolpropane, and/or polycarbonate esters having a hydroxyl group at the end;
Polyester-type polyols such as These polyester polyols can be produced by known methods. For example, in the case of adipic acid-based polyester polyols, a known method is used in which adipine [1 mol, diethylene glycol 1 mol, and trimethylolpropane 0.06 mol are reacted in a ratio of 0.06 mol] is used. The following methods can be mentioned.

In the present invention, in a urethane resin whose main components are an aliphatic isocyanate that has no unsaturated bonds other than isocyanate groups and a polyester polyol, the main component is an aliphatic isocyanate that has no unsaturated bonds other than isocyanate groups. This means that the molar weight of the isocyanate and the polyester type polyol is 80 molar weight or more, and the A component resin is, for example, 0.4 mol of an aliphatic isocyanate having no unsaturated bond other than the above-mentioned isocyanate group and a polyester. A known addition/condensation process of 0.5 mol of type polyol and 0.1% chain extender (e.g. butylene glycol)
Examples include those obtained by crosslinking reactions and the like.

The weight average molecular weight (Mw) of the A-component resin is preferably 70,000 to 200,000 because it can easily exhibit excellent performance, and more preferably 70,000 to 150,000.

The ultraviolet absorber B component represented by the general formula [I] used in the present invention needs to have a molecular weight of 350 or more. Those with a molecular weight of less than 350, for example,
2-(2'-Hydroxy-5-methyl-phenyl)benzotriazole [e.g., trade name Tinupin P: molecule [
No. 225) has poor weather resistance and causes surface whitening, pluming, etc., as in the comparative example described below. Also, it is said to improve weather resistance, for example, 2-(2-hydroxy-
3,5-sheet-t-butyl-phenyl)-5-chlorobenzotriazole (for example, trade name Tinuvin 327; molecular weight 357.5) lacks compatibility with the A component resin used in the present invention and has poor weather resistance. In addition to this problem, molded articles containing the ultraviolet absorber have the disadvantage of being colored from the initial stage.

In the above general formula CI), the molecular weight satisfies the condition of 350 or more, R1 or R, may be the same or different, and each has a branched chain and has 2 to 12 carbon atoms. It represents an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group, which may have a substituent such as a methyl group or a butyl group. There is no problem. Examples of these groups include ethyl group, butyl group (n-13-1i-11-), amyl group (n-1
alkyl groups such as hexyl group (n-1 etc.), octyl group (1-1 etc.), nonyl group, dodecyl group; cycloalkyl group such as cyclopropyl group, cyclohexyl group; phenyl group , aryl groups such as cumenyl group, tolyl group, and xylyl group; aralkyl groups such as be/zyl group, methylbenzyl group, 7enethyl group, phenylpropyl group, and 2-phenylpropyl group;
2-(2'-hydroxy-
3-5'-di-2-phenylpropyl-phenyl)benzotriazole [trade name, Tinuvin 234; molecular weight 44
7], 2-(2'-hydroxy-3-5'-di-t-amyl-phenyl)hen/ ) IJ azole [trade name,
Tenubin 328; molecular weight 351], and these ultraviolet absorbers are easily available and can be used particularly preferably. Also, if desired,
There is no problem in using two or more of these UV absorber B components in combination.

The weight average molecular weight (Mw) of the deterioration inhibitor C component containing the structural unit represented by the general formula [■] in the repeating unit used in the present invention is required to be 2,500 or more. If the Mw is less than 2,500, the surface smoothness decreases, and problems such as thinning of the molded article in particular tend to become serious, which is not preferable.

In the above general formula (Ir), Mw satisfies the condition of 2500 or more; R8, R,, R, or R6 may be the same or different, and each has a hydrogen atom or 1 carbon atom. ~3 represents an alkyl group; X represents a succinyl group, a glutaryl group, or an adipoyl group; n represents an alkyl group of 2 to
represents an integer of 4, where the number of carbon atoms is 1
The alkyl group of ~3 refers to a methyl group, an ethyl group, or a propyl group (n-1i-).

As the C component containing the structural unit represented by the general formula [■] in the repeating unit used in the present invention, R3,
R4, R, and R6 are the same methyl group, and n is 2
, X is a succinyl group, a light yellow powdery molecule [more than 3000, for example, the trade name Tinuvin 622 L
D can be preferably used.

Furthermore, as the C component used in the present invention, the general formula (n
) The repeating unit containing the structural unit represented by the following general formula, (wherein; R1, R1, R1 or R6, X and n are as defined above: R?s n, , R, Or, Rlo has the same meaning as the definition of R3, R4, Rs or R6: m represents an integer of 4 or more.) Those represented by the following can be used more preferably.

As such C component, Mw is 2500 or more, n is an integer of 2, and X is a succinyl group, for example, a product under the trade name 5AN
OL LS 622 LD (manufactured by Sanki ■) [dimethyl succinate/1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-titramethylpiperidine polycondensate] is preferably used.

In addition, if desired, as the C component, the above general formula [■]
It is even more acceptable to use the compound represented by the above formula and the compound represented by the general formula 1] in combination.

The urethane resin composition for molding of the present invention has 1. In order to impart the above-mentioned excellent properties to the molded product, an ultraviolet absorber component B having a molecular weight of 350 or more represented by the general formula [I] and a deterioration inhibitor having a Mw of 2500 or more represented by the general formula CIT) are required. The ratio of parts by weight of C component or/and C component preferably having a weight of 2,500 or more represented by the general formula 1] is 20:80 to 80:20, and the total of the B component and the C component The weight part is based on 100 weight parts of A component resin,
It is necessary to contain 0.45 parts by weight or more. Even if the ratio of parts by weight of the B component and the C component deviates from the range of 20:80 to 80:20, even if the total parts by weight of the B component and the C component is less than 0.45, A synergistic effect cannot be obtained, and it becomes difficult to impart various performances such as the above-mentioned excellent weather resistance to the molded article.

The urethane resin composition for molding of the present invention is preferably molded into a non-foamed film or sheet having a thickness of about 30 .mu.m to about 2000 .mu.m.

At this time, the total maximum parts by weight of component B and component C with respect to the resin of component A is not particularly limited, and as described above, 0.45 parts by weight or more is mixed and modified, but the desired molded product is For example, in the case of chipping-resistant films for automobiles, or films and sheets to be laminated onto plates and containers such as glass and plastic bottles, the desired thickness of the molded product generally varies depending on the purpose. Corresponding to the desired thickness of the molded body, where the body thickness μ) is t, the total weight part W of the B component and the C component is determined by the following formula for 100 parts by weight of the A component resin: 10ρoss t W =0.45 + 2・e ・−・−[JV
] It is particularly preferable to use a molding urethane resin composition containing at least the weight part calculated by:

Molded from a molding urethane resin composition that satisfies the conditions of the above-mentioned formula discovered by the present inventors, the thickness is about 50 μ to about 10 μm.
00μ film/sheet, etc., especially thickness of about 50μ to about 5
00μ films and sheets are suitable for outdoor use as they can exhibit various performances such as excellent weather resistance.

As can be seen from the examples described later, if the total weight part W calculated using the formula (5) is also slightly excessive, excellent weather resistance, etc., which could not be achieved conventionally, can be obtained. The number of parts by weight to be added is 60 of the calculated total weight part W.
An amount of about 1 or less is economically preferable, and the object of the present invention can be fully achieved. Thickness t of the molded body of the film/sheet in the non-foamed state calculated by the above formula
To specifically show the total weight part W in , the thickness t is 50μ
, 100μ, 200μ, and 500μ, the total weight part W is 1.97.1.6.1811 and 0.57, respectively.

In the urethane resin composition for molding of the present invention, the B component and the C component can be blended in the manufacturing process of the A component resin, or the B component and the C component can be blended into the A component resin using a V-type blender, a Banbury blender, etc. mixer, Henschel mixer,
It can also be made using a mixing means such as a tumbler mixer.

The urethane resin composition for molding of the present invention may contain other additives, such as antioxidants, lubricants, pigments, fillers, flame retardants, polishing agents, etc., if desired.

Examples of the antioxidant that can be added to the urethane resin composition for molding of the present invention include 2,2-methylene-bis-(4-
Methyl-6-tert-butylphenol), triethylene glycol and 3-(3-tert-butyl-4-hydroxy-5-methyl-phenyl)propionate, 1.3.5
-trityl-2,4,6-)lis(3,5-di-t-butyl-4-hydroxybenzyl)hensen,tetrakis/methylene-3-(3,5-di-t-butyl-4'-hydroxy phenyl) propionate/methane, etc.

Examples of lubricants that can be blended include montanic acid ester wax (trade name Hoechst Wax, manufactured by Hoechst).
waxes such as oxystearamide, fatty acid amide such as oleic acid amide, polyethylene wax, and the like.

〔Effect of the invention〕

The urethane resin composition for molding of the present invention can be molded by various molding methods, and can be molded into molded objects such as coating materials, covering materials, laminated materials, heat insulating materials, fibers, etc., preferably into molded objects such as films and sheets. When doing so, the B component and C component act synergistically on the A component resin, and exhibit a high degree of weather resistance that is particularly suitable for molded products for outdoor use, which could not be achieved with conventional urethane resin compositions for molding. However, it exhibits a remarkable effect of inhibiting thickness reduction, discoloration/discoloration, blooming, whitening, adhesion, etc., and maintains surface smoothness, so its industrial significance is extremely large.

The present invention will be further explained below with reference examples, working examples, and comparative examples, but the present invention is not limited to the following examples. weather
A meter test was conducted.

(1) Accelerated deterioration test method (hereinafter sometimes abbreviated as QUV test) A film or sheet made from a urethane resin composition is
Using a weather meter manufactured by Q Panel Company, an accelerated deterioration test was conducted under the conditions of lamp lighting time of 8 hours, temperature of 70°C, lights out and dew condensation time of 4 hours, and temperature of 50°C.

(11) Weather meter test method (hereinafter sometimes abbreviated as aM test) Using the same film/sheet as used in the QUV test as a sample, using a Sunshine weather meter manufactured by Suga Test Instruments, water spray was applied. A weather meter test was conducted according to the test method of JIS D0205, except that the test was carried out for 18 minutes out of 120 minutes.

According to the above two test methods, durability t- of about 1000 hours or more is required to determine that the product can be used outdoors and is practical. During the weather resistance test, the test sample is periodically observed with the naked eye, and the thickness reduction, coloration, blooming, surface smoothness, whitening, and stickiness of the sample are investigated, and when no change is observed in the sample, The results were evaluated by grading Δ when a slight change was observed, and × when a clear change was observed.

[Creation of urethane resin]

Reference Example 1 985 parts by weight of a polyester type polyol obtained by reacting 1,4-butanediol and adipic acid as main components, and 3 parts by weight of 4,4-dicyclohexylmethane diisocyanate.
By reacting 40 parts by weight with 90 parts by weight of 1,4-butanediol, a chain extender, a urethane resin having an Mw of about 94,000 was prepared.

Reference Examples 2 to 3゜A total of 1090 parts by weight of adipic acid-based polyester polyol and chain extender 1,4-butanediol were used in the same manner as in Reference Example 1, and as an isocyanate compound,
In Reference Example 2, 225 parts by weight of hexamethylene diisocyanate was reacted, and in Reference Example 3, 335 parts by weight of 4,4-diphenylmethane diisocyanate were reacted.
About 74,000 Mw, in reference example 3, about 112,000 Mw
I created each of them.

Examples 1 to 10 and Comparative Examples 1 to 8 As the urethane resin A component, those with specific weight average molecular weights prepared in Reference Examples 1 and 3 were used, and as the ultraviolet absorber B component, Tinuvin 234 (trade name) was used. (2-Hydroxy-3,5-di-2'-phenylpropyl-phenyl)benzotriazole], trade name Tinuvin 328C2-
(2-Hydroxy-3',5'-di-t-amyl-phenyl)benzotriazole], trade name Tinupi/P [2-
(2'-Hydroxy-5'-methyl-phenyl)benzotriazole], the product name Tinuvin 622-LD is represented by the above general formula [■] as the deterioration inhibitor C component, and the product is represented by the above general formula 1]. Famous Sanol LS 622L
D[poly(1-diethyl adipe)) 2,2,6.
6-tetramethyl-4-oxypiperazine compound] and as a similar deterioration inhibitor, the trade name Sanol LS770 [: bis(2,2-6-6-tetramethyl-4-piperidyl)
100 parts by weight of urethane resin component A, and the total number of parts by weight of component B and component C shown in Table 1 and the ratio of parts by weight of component B and component C to 100 parts by weight of urethane resin component A. It was created using a v-type blender.

Next, in order to conduct a weather resistance test on the above-mentioned urethane resin composition for molding, the resin composition was subjected to a press plate method (preheated on a press plate at 140°C for 5 minutes; then, a pressure of 30 to 7~ was applied several times to evacuate the air). ;Finally 30 kf/d, 155℃, 10
The film and sheet were formed into a film and sheet having a thickness t shown in Table 1.The QUV test and WOM test described above were conducted using the film and sheet thus obtained as samples. The results of this weather resistance test are shown in Table 2.

As Comparative Example 9, a urethane resin composition for molding was prepared in which 1.2 parts by weight of Tinuvin 234, which was the B component, was blended alone without Sanol LS 622LD, which was the C component in Example 1; as Comparative Example 10, B in Example 1
A molding urethane resin composition was prepared in which 1.2 parts by weight of Sanol LS622LI (component C) was blended alone without the component Tinuvin 234, and the thickness of the film and sheet were 208μ and 213μ, respectively. It was molded and subjected to a weather resistance test, but there was no mutual effect on weather resistance, and the various performances were similar to the test results of Comparative Example 7 in Table 2. It could not be used as a urethane resin composition.

As can be seen from the weather resistance test results shown in Table 2, the urethane resin composition for molding of the present invention, particularly the ultraviolet absorber component B and the deterioration inhibitor C component, satisfy the specific conditions of the present invention, and Example 1 in which the total weight part W satisfies the above general formula
-10 exhibited excellent weather resistance performance that cannot be achieved with conventional urethane resin compositions for molding, and demonstrated its effectiveness in molded products for various outdoor applications.

Although the total weight part W of Example 10 is less than the total weight part W calculated by the above general formula, the performance is practical and exceeds that of conventional molding urethane resin compositions. Indicated.

On the other hand, various performances of films and sheets using the urethane resin compositions for molding shown in Table 1 that do not satisfy the specific conditions of the urethane resin composition for molding of the present invention are as shown in Table 2. The performance is significantly worse than those of 1 to 9,
When the isocyanate component of the urethane resin is 4,4-diphenylmethane diisocyanate, which is a so-called aromatic polyisocyanate, problems such as coloring are observed in a short time, and when the Mw of the deterioration inhibitor C component is low, the thickness decreases. In addition, when Tinuvin P, a low-molecular-weight ultraviolet absorber component B, is used, problems such as blooming occur in a short period of time in addition to a decrease in thickness, and as in Comparative Examples 9 and 10 mentioned above, The molded product could not be put to practical use as a molded product for outdoor use.

Example 11 100 parts by weight of the urethane resin prepared in Reference Example 2 was dissolved in 380 parts by weight of chloroform, and then 0.8 parts by weight of Tinupin 234 (trade name) and Sanol LS622LJ (trade name) were added to the urethane resin. After adding t-0.4 parts by weight and stirring and dissolving, the solution was cast onto release paper, dried at about 25°C, and formed into a film with a thickness of 202 μm.

The film was subjected to the QUV test and WOM test described above.

The results were good up to 2700 hours in both the QUV test and the WOM test. Although no decrease in thickness was observed even after 3000 hours, at this time, some coloring and whitening were observed in the QUV test, and a slight decrease in surface smoothness and occurrence of pluming were observed in the WOM test.

Example 12 To 500 parts by weight of a polyester type polyol obtained by reacting 1,4-butanediol and adipic acid as main components, 3 parts of 4,4-synchrohexylmethane diisocyanate was added.
To the prepolymer obtained by reacting 00 parts by weight, 100 parts of 1,4-butanediol, 16 parts of Tinuvin 234 (trade name), and 16 parts of Sanol LS622L (trade name) were added in advance.
62 parts by weight of a solution containing D at a weight ratio of 8 was added and reacted to produce a liquid urethane resin composition having an Mw of about 129,000.

In this composition, the ultraviolet absorber component B corresponds to 0.93 parts by weight and the deterioration inhibitor C component corresponds to 0.47 parts by weight based on 100 parts by weight of the urethane resin.

Immediately after the reaction, the resin liquid was cast onto release paper.

Then, using the same press plate method as described above, it was formed into a film having a thickness of 213 μm.

The film was subjected to the QUV test and WOM test described above.

Even after 3000 hours, there was no decrease in thickness in any test.
It exhibited excellent performance without coloring, blooming, whitening, etc.

Claims (1)

[Scope of Claims] 1) The ratio of ultraviolet absorber B component and deterioration inhibitor C component to 100 parts by weight of urethane resin component A is 20:80 to 80:20, and A urethane resin composition for molding, characterized in that the total weight part of the B component and the C component is 0.45 parts by weight or more. A. A urethane resin whose main components are an aliphatic isocyanate and a polyester polyol, which have no unsaturated bonds other than isocyanate groups. B, an ultraviolet absorber having a molecular weight of 350 or more and represented by the following general formula. ▲ There are mathematical formulas, chemical formulas, tables, etc. (Represents a good alkyl group, cycloalkyl group, aryl group, or aralkyl group.) C. A deterioration inhibitor having a weight average molecular weight of 2,500 or more and containing a structural unit represented by the following general formula in the repeating unit. ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[II] (In the formula; R_3, R_4, R_5 or R_6 may be the same or different, and each is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; represents a succinyl group, a glutaryl group, or an adipoyl group; n is an integer of 2 to 4.) 2) The repeating unit of the deterioration inhibitor has the following general formula, ▲ mathematical formula, chemical formula, table, etc. ▼... [III] (In the formula; R_3, R_4, R_5 or R_6, X and n are as defined above; R_7, R_8, R_
9 or R_1_0 has the same meaning as the definition of R_3, R_4, R_5 or R_6; m represents an integer of 4 or more; ) The urethane resin composition for molding according to claim 1, which is represented by: 3) The total weight part W of the B component and the C component is a molded product, and when the thickness (μ) of the molded product is t, the following formula is calculated for 100 parts by weight of the urethane resin A component: , W=0.45+2・e^-^0^. ^0^0^5^5t
The urethane resin composition for molding according to claim 1 or 2, which contains at least the weight part calculated by [IV].