JPS633051A - Halogen-containing resin composition having improved weather resistance - Google Patents

Abstract

PURPOSE:The titled resin composition having thermal stability in processing, antistatic properties and extremely improved weather resistance as well, obtained by stabilizing a halogen-containing resin with an organotin maleate compound in the presence of a specific boric acid ester compound. CONSTITUTION:100pts.wt. halogen-containing resin is blended with (A) an organotin maleate compound such as dimethyltin bis(methyl maleate), dibutyltin maleate, etc., and (B) a boric acid ester compound shown by formula I and/or formula II (R<1>-R<4> are 1-30C alkyl, alkenyl, aralkyl, aryl or cycloalkyl; R<5> is residue after removal of two OH from polyhydric alcohol containing 2-6 OHs; X and Y are residue after removal of each H from different two carbons of 2-10C alkane; m and n are >=1) in a weight ratio of the component A:B=99.95:0.05-50:50 in an amount to give 0.1-20pts.wt. total amounts of the components A and B.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to a halogen-containing resin composition with excellent weather resistance, and when the halogen-containing resin is stabilized with an organotin maleate compound, weather resistance is required. It can be used for molded products such as films, sheets, corrugated sheets, industrial boards, and various irregularly shaped products.

[Conventional technology]

In general, organotin maleate compounds are used in many of the above-mentioned products as effective stabilizers for improving the thermal stability and weather resistance of chlorine-containing vinyl resins. Various techniques have been disclosed to further improve the thermal stability and weather resistance of chlorine-containing vinyl resins by using this organotin maleate compound in combination with other compounds. Among them, techniques for improving the thermal stability of halogen-containing resins by using an organotin maleate compound and a boric acid ester compound in combination are disclosed in JP-A-53-+11346 and JP-A-54-13804.
No. 7, No. 55-25424, and No. 55-27351 are known, and Japanese Patent Application Laid-open No. 56-2335 is known as a technique with improved antistatic properties.

[Problems that the invention attempts to solve]

The above-mentioned halogen-containing resin composition that uses a combination of a boric acid ester and an organotin maleate compound, which has been conventionally used, has poor weather resistance even though the thermal stability and antistatic ability during processing are improved. It was unsatisfactory for use in the required products. Therefore, a halogen-containing resin composition having even better weather resistance than conventional ones has been awaited.

[Means for solving problems]

As a result of intensive research from this viewpoint, the present inventors found that when stabilizing a halogen-containing resin with an organotin maleate compound, -general formula (+) and/or (2) -OR' H) R'lXO+lB ,. □.

R'O+YO7B-:::R5(2) (In formulas (+) and (2), R', R", R', and R' are alkyl groups, alkenyl groups, and aralkyl groups having 1 to 30 carbon atoms. group, aryl group and cycloalkyl group, RS is a residue obtained by removing two hydroxyl groups from a polyhydric alcohol having 2 to 6 hydroxyl groups, R', R'.

R' and R may be the same or different. X and Y are two different carbon atoms of an alkane having 2 to 10 carbon atoms,
Residues from which one hydrogen atom has been removed, m and n each represent an integer of 1 or more. It has been discovered that a halogen-containing resin composition with significantly improved weather resistance can be obtained by adding at least one of the boric acid ester compounds shown in ), and the present invention has been completed.

Examples of the halogen-containing resin stabilized by the present invention include commonly used halogen-containing resins, such as vinyl chloride resin, vinyl bromide resin, vinylidene chloride resin, chlorinated ethylene resin, and chlorinated propylene resin. Resin, post-chlorinated vinyl chloride resin, vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-ethylene copolymer resin, vinyl chloride-propylene copolymer resin, vinyl chloride-styrene copolymer resin, vinyl chloride-vinylidene chloride copolymer resin , vinyl chloride-ethylene-vinyl acetate copolymer resin, and the like.

Furthermore, blend polymers mainly composed of vinyl chloride resin and other copolymer resins, such as vinyl chloride resin and acrylonitrile-butadiene-styrene copolymer resin, methyl methacrylic-butadiene-styrene copolymer resin, styrene-
Examples include blend polymers with acrylonitrile copolymer resins, acrylonitrile-butadiene copolymer resins, ethylene-vinyl acetate copolymer resins, and the like.

The organotin maleate compounds used in the present invention include commonly used compounds, such as - general formulas (3) and (4) (in formulas (3) and (4)). ,R
6 is an alkyl group, a cycloalkyl group, an alkenyl group,
Aralkyl group, alkoxyalkyl group, R7 is an alkyl group having 1-12 carbon atoms, A is oxygen or 100CC
H= group represented by C)lCoo-, p is O or t
, q represents an integer of 1 to 10. ) and the like.

Examples of the organotin maleate compounds represented by the general formula (3) include the following.

Dimethyltin bis(methyl maleate), dimethyltin bis(ethyl maleate), dimethyltin bis(isopropyl maleate), dimethyltin bis(butyl maleate)
, dimethyltin bis(hexyl maleate), dimethyltin bis(octyl maleate), dimethyltin bis(isooctyl maleate), dimethyltin bis(2-ethylhexyl maleate), dimethyltin bis(decyl maleate), dimethyltin bis(decyl maleate) (dodecyl maleate), dimethyltin bis(tridecyl maleate), dimethyltin bis(
octadecyl maleate), dimethyltin bis(oleyl maleate), dimethyltin bis(pennormaleate)
, dimethyltin bis(cyclohexyl maleate), dimethyltin bis(methoxybutyl maleate), dibutyltin bis(methyl maleate), dibutyltin bis(ethyl maleate), dibutyltin bis(propyl maleate)
, dibutyltin bis(isopropyl maleate), dibutyltin bis(butyl maleate), dibutyltin bis(amyl maleate), dibutyltin bis(hexyl maleate), dibutyltin bis(heptyl maleate), dibutyltin bis(octyl maleate) ate), dibutyltin bis(isooctyl maleate), dibutyltin bis(2-ethylhexyl maleate), dibutyltin bis(nonyl maleate), dibutyltin bis(decyl maleate), dibutyltin bis(dodecyl maleate), dibutyltin bis (tridecyl maleate), dibutyltin bis(octadecyl maleate), dibutyltin bis(allyl maleate),
Dibutyltin bis (oleyl maleate), dibutyltin bis (benzyl maleate), dibutyltin bis (cyclohexyl maleate), dibutyltin bis (methoxybutyl maleate), dioctyltin bis (ethyl maleate)
, dioctyltin bis(propyl maleate), dioctyltin bis(isopropyl maleate), dioctyltin bis(butyl maleate), dioctyltin bis(hexyl maleate), dioctyltin bis(octyl maleate), dioctyltin bis( isooctyl maleate),
Dioctyltin bis(2-ethylhexyl maleate),
Dioctyltin bis(decyl maleate), dioctyltin bis(dodecyl maleate), dioctyltin bis(tridecyl maleate), dioctyltin bis(octadecyl maleate), dioctyltin bis(oleyl maleate), dioctyltin bis(benzyl maleate) ate), dioctyltin bis(cyclohexyl maleate), dioctyltin bis(methquin butyl maleate), dilauryltin bis(ethyl maleate), dilauryltin bis(isopropyl maleate), dilauryltin bis(butyl maleate), Dilauryltin bis(hexyl maleate), dilauryltin bis(octyl maleate), dilauryltin bis(isooctyl maleate), dilauryltin bis(
2-ethylhexyl maleate), dilauryltin bis
(decyl maleate), dilauryl tin bis (dodecyl maleate), dilauryl tin bis (tridecyl maleate), dilauryl tin bis (octadecyl maleate), dilauryl tin bis (oleyl maleate), dilauryl tin bis (benzyl maleate), Dilauryltin bis(cyclohexyl maleate), dilauryltin bis(methoxybutyl maleate), bis(dimethyltin methyl maleate) maleate, bis(dimethyltin ethyl maleate) maleate, bis(trimethyltin isopropyl maleate) maleate, bis (Dimethyltin butyl maleate)
Maleate, bis(dimethyltin hexyl maleate) maleate, bis(dimethyltin octyl maleate) maleate, bis(dimethyltin isooctyl maleate) maleate, bis(dimethyltin 2-ethylhexyl maleate) maleate, bis(dimethyltin decyl maleate) Maleate, bis(dimethyltin dodecyl maleate) maleate, bis(dimethyltin tridecyl maleate) maleate, bis(trimethyltin octadecyl maleate) maleate, bis(dimethyltin oleyl maleate) maleate, bis(dimethyltin benzyl maleate) )
Maleate, bis(dimethyltin cyclohexyl maleate) maleate, bis(dimethyltin methquine butyl maleate) maleate, bis(butyltin methyl maleate) maleate, bis(dibutyltin ethyl maleate) maleate, bis(dibutyltin propyl maleate) Eight)
Maleate, bis(butyltin isopropyl maleate) maleate, bis(butyltin butyl maleate) maleate, bis(butyltin amyl maleate) maleate, bis(dibutyltin hexyl maleate) maleate, bis(dibutyltin hexyl maleate) maleate, Bis(butyltin octyl maleate) maleate,
Bis (dibutyltin isooctyl maleate) maleate, bis (dibutyl 82-ethylhexyl maleate)
Maleate, bis(dibutyltin nonyl maleate) maleate, bis(dibutyltin denyl maleate) maleate, bis(dibutyltin dodecyl maleate) maleate, bis(dibutyltin tridecyl maleate) maleate, bis(dibutyltin octadecyl maleate) maleate, bis (dibutyltin allyl maleate) maleate, bis(dibutyltin oleyl maleate) maleate,
Bis(dibutyltin benzyl maleate) maleate, bis(dibutyltin cyclohexyl maleate) maleate, bis(butyltin methoxybutyl maleate) maleate, bis(dioctyltin ethyl maleate) maleate, bis(dioctyltin propyl maleate) maleate , bis(dioctyltin isopropyl maleate) maleate, bis(dioctyltin butyl maleate) maleate, bis(dioctyltin hexyl maleate) maleate, bis(dioctyltin octyl maleate) maleate, bis(dioctyltin ictyl maleate) maleate , bis(dioctyltin 2-ethylhexyl maleate) maleate, bis(dioctyltin decyl maleate) maleate, bis(dioctyltin dodecyl maleate) maleate, bis()octyltin tridecyl maleate) maleate, bis(dioctyltin octadecyl maleate) ) maleate, bis(dioctyltin oleyl maleate) maleate, bis(dioctyltin pennormaleate) maleate, bis(dioctyltin cyclohexyl maleate) maleate, bis()octyltin methoxybutyl maleate) maleate, bis(dilauryltin) Ethyl maleate) maleate, bis(dilauryltin isopropyl maleate) maleate, bis(dilauryltin butyl maleate) maleate, bis(dilauryltin hexyl maleate) maleate, bis(dilauryltin octyl maleate) maleate, bis(dilauryltin isopropyl maleate) maleate) maleate, bis (
dilauryltin 2-ethylhexyl maleate) maleate, bis(dilauryltin decyl maleate) maleate, bis(dilauryltin dodenyl maleate) maleate, bis(dilauryltin tridecyl maleate) maleate, bis(dilauryltin octadecyl maleate) maleate, Bis(dilauryltin oleyl maleate) maleate, bis(dilauryltin benzyl maleate) maleate, bis(dilauryltin chlorohexyl maleate) maleate, bis(dilauryltin methoxybutyl maleate) maleate, bis(dimethyltin methyl maleate) oxide , bis(dimethyltin methyl maleate) oxide, bis(dimethyltin butyl maleate) oxide, bis(dimethyltin isooctyl maleate) oxide, bis(dimethyltin benzyl maleate)
oxide, bis(dibutyltin methyl maleate) oxide, bis(butyltin butyl maleate) oxide, bis(dibutyltin isooctyl maleate) oxide, bis(dibutyltin benzyl maleate) oxide, bis(dioctyltin butyl maleate) ) oxide, bis(dioctyltin isooctyl maleate) oxide, bis(dioctyltin pennormaleate) oxide, bis(dilauryltin butyl maleate) oxide, bis(dilauryltin isooctyl maleate) oxide, bis(dilauryltin pennormaleate) oxide benzyl maleate) oxide, etc.

Examples of the tin maleate compounds represented by the general formula (4) include the following. These include dimethyltin maleate, dibutyltin maleate, dioctyltin maleate, dilauryltin maleate, and polymers thereof.

The boric acid ester compound used in the present invention has the general formula (
1) and/or (2) 10R1 R'O+X l-, B,. □, (1) R'O
±YO2B cod,,R'(2)II'I (In formulas (1) and (2), R', R', R3, and R' are
Alkyl group, alkenyl group, aralkyl group, aryl group, and cycloalkyl group having 1 to 30 carbon atoms, R' is a residue obtained by removing two hydroxyl groups from a polyhydric alcohol having 2 to 6 hydroxyl groups, R1, Rt.

R' and R' may be the same or may be holes. X and Y are two different carbon atoms of an alkane having 2 to 10 carbon atoms,
The residues, m and n, each excluding one hydrogen atom, are:
Indicates an integer greater than or equal to 1. ) Rl, Rt.

R″′ and R4 are alkyl groups, alkenyl groups, aralkyl groups, aryl groups, and cycloalkyl groups having 1 to 30 carbon atoms, examples of which include methyl, ethyl, propyl,
Isopropyl, butyl, butyl, secondary
Butyl, tert-butyl, pentyl, hexyl,
Heptyl, octyl, isooctyl, 2-ethylhexyl, nonyl, desol, dodecyl, tridecyl,
hexadecyl, octadecyl, eicosyl, tocosyl,
Triacontyl, vinyl, 1-propenyl, 2-propenyl, ]-butenyl, 2-butenyl, pentenyl, heptenyl, decenyl, dodecenyl, pentadecenyl, heptadecenyl, octadecenyl, 9-octadecenyl, nonadecenyl, tococenyl, benzyl, phenethyl, phenyl, tolyl, Mention may be made of groups such as xoryl, butylphenyl, octylphenyl, nonylphenyl, ternary butylphenyl, cyclohexyl and the like. Among these, preferred examples include methyl, ethyl, butyl, 2-ethylhexyl, tridecyl, octadecyl, 2-ethylhexyl,
-propenyl, l-butenyl, 9-octadecenyl, benzyl, phenyl, tolyl, ternary-butylphenyl, nonylphenyl, cyclohexyl, etc., the most preferred examples being methyl, 2-
Examples include groups such as ethylhexyl, 2-propenyl, benzyl, phenyl, and cyclohexyl.

Further, R5 is not limited in the number of carbon atoms, but has about 2 to 30 carbon atoms, preferably 2 to 22 carbon atoms, and is a residue obtained by removing two hydroxyl groups from a polyhydric alcohol having 2 to 6 hydroxyl groups. Examples of the polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1.2-butylene glycol, 1.3-butylene glycol, and 2.3-butylene glycol. Butylene glycol, isobutylene gellicol, 1,4-butanediol, neopentyl glycol, 1,5-bentanediol, 1゜6-hexaneol, 2-methyl-2,
4-bentanediol, 2.2.4-)dimethyl-1,
3-bentanediol, I,8-octanediol, glycerin, trimethylolmethane, trimethylolethane, trimethylolpropane, trimethylolbutane,
Examples include diglycerin, pentaerythritol, aravit, atonite, dipentaerythritol, sorbitol, mannitol, and the like. Among these, examples of preferable polyhydric alcohols include ethylene glycol, propylene glycol, trimethylene glycol,
1.2-butylene glycol, 1.3-butylene glycol, 2.3-butylene glycol, isobutylene glycol, neopentyl glycol, 2-methyl-2,4
-bentanediol, glycerin, trimethylolpropane, pentaerythritol, etc., and the most preferred examples are ethylene glycol, trimethylene glycol,! , 3-butylene glycol, 2.3
-Polyhydric alcohols such as butylene gellicol, trimethylolpropane, and pentaerythritol can be mentioned.

Moreover, X and Y are 2 different alkanes having 2 to 10 carbon atoms.
It is a residue obtained by removing one hydrogen atom from each carbon atom, and examples of the alkanes include ethane, propane, butane, 2-methylpropane, pentane, 2-methylbutane, and 2.2-methylpropane. , hexane, 2
-Methylbentane, 3-methylpentane, 2.2-dimethylbutane, heptane, 2-methylhexane, 3-methylhexane, 3-ethylpentane, 2.2-dimethylbencune, 2.3-dimethylbencune, 2 .4-Dimethylpentane, 3.3-dimethylbencune, 2,2.3-trimethylbutane, octane, 2-methylhebutane, 3-
Methylhebutane, 2.2-dimethylhexane, 2.3-
Dimethylhexane, 2.5-dimethylhexane, 3゜4
-dimethylhexane, 2,2.3-)dimethylbencune, 2.2.4-trimethylpentane, 2゜3.3-trimethylpentane, 2.3.4-trimethylpentane, 3
-ethylhexane, nonane, 2-methyloctane, 3-
Methyloctane, 4-methyloctane, decane, 2-methylnonane, 3-methylnonane, 4-methylnonane, 5
-Methylnonane, etc. can be mentioned. Among these, preferred examples of alkanes include ethane, propane, butane, 2-methylpropane, pentane, 2-methylbutane, 2,2-dimethylpropane, 2-methylpentane,
Examples include 3-methylpentane, 2,2-dimethylbutane, and the most preferred examples include alkanes such as ethane, propane, butane, and pentane.

Further, m and n are integers of 1 or more, and although there are no special restrictions, they are usually integers of 1 to 10, preferably 1 to 3.
is an integer.

Specific examples of the boric acid ester compounds used in the present invention include, but are not limited to, the following. That is, (a) cHffocH, cH, oB:'$”-Ze certain hill (
. H3) 3(a) ctHsoc, cH, oB: 4”-
Damaki-ri.

(T) C, H, 0 (CIT, CH, 0) 2Bζ meter, Yumon? ■・ (1) C113(CHI), C)1=C)I(CH,
), CH,0(CH,C)1.0), audience with B'H3 CH.

(Te) C, J, 70 (C11, C1'l, 0), B
:823■:/Ctemura 119・H・ ()) (C)13)3C-Q-QC)I,CLC)
! , OB', g28L9H・ (su) Q-CI, QC) I, CH, CH, CH,
8 in OB and I(s (nu)〈:=nーC1(,0(C)1.CI(,CB,
CB, O), Bgu322H:;CL9H・ (ne) ○-0(CH, CIl, CI, CH, 0)y
Bte8TenCL9H・ () ) C, H2O (CI, CI, CH, CH2
0)3Bte8]8HsaH.

(c) C,,H,,0(CI(,CH,CHfC
Examples include H, 0) 3B, 823■:'/C, 3 system δ□, and two or more of these can also be used in combination.

The amount of the organic tin maleate compound and boric acid ester compound used in the present invention is not particularly limited, but the total amount of the organic tin maleate compound and the boric acid ester compound is based on 100 parts by weight of the halogen-containing resin. 0.1 ~
The amount may be about 20 parts by weight, preferably 1 to 8 parts by weight.

If the amount added is less than 0.1 parts by weight, the weather resistance will not be improved, and if it is more than 20 parts by weight, the expected effect will not be seen. ,
There is no particular restriction on the ratio of the organic tin maleate compound and the boric acid ester compound, but the ratio of organic tin maleate compound to boric acid ester compound = 99.95:
About 0.05 to 50:50, preferably 99:1 to 7
It was 0:30. 0.05 w of boric acid ester compound
Below t%, no synergistic effect on weather resistance is observed, and at 50vt%
The expected effects cannot be seen in the above cases.

In carrying out the present invention, the halogen dowel resin, the organotin maleate compound, and the boric acid ester compound used in the present invention may be mixed in a known mixer such as a Henschel mixer or a Banbury mixer. Alternatively, an organotin maleate compound and a boric acid ester compound may be mixed together in advance and added to the halogen-containing resin.

The resin composition of the present invention may further include a metal soap, if necessary.
plasticizer, antioxidant, epoxy compound, ultraviolet absorber,
Lubricants, pigments, fillers, processing aids, etc. can be added.

The present invention will be specifically explained below with reference to Examples, but the present invention is not limited thereto. In the examples, parts refer to parts by weight.

Example 1 Vinyl chloride resin [GeonlQ3 manufactured by Nippon Zeon Co., Ltd.
El)] 100B, dibutyltin bis(butylmaleny)) 2 near part and the additives shown in Table 1 were mixed together at 170°C for 5 minutes using an 8-inch test roll, and the mixture was kneaded to a thickness of 0. A .5-day sheet was prepared. This sheet was pressed at 100 Kg/cl' for 10 minutes at +50°C, and then cut into a size of 30 mm x 100 mm to produce four sheets.

Each of the obtained sheets was pasted on an exposure stand facing south with an inclination angle of 45°C. After three years, the pasted sheets were sampled and the state of discoloration was observed and evaluated.

The state of discoloration was evaluated using A, B, and C below.

A: There is almost no discoloration.

B: Whitening.

C: It has become brown.

As can be seen from [Table 1], the resin composition of the present invention to which a boric acid ester compound is added has extremely excellent weather resistance.

Similar results were obtained when other known boric acid esters such as the following compounds were used in place of the tristearylboric acid ester of Sample No. 4.

O0H (R=n-butyl, lauryl, stearyl (excluding (C)), nclohexyl, oleyl, ethylene glycol, and methoxybuquinol) (R'-butylenyl, R"
=stearyl) [Table 1] Sample Nos. 1 to 4 are comparative examples. No. 5 to 9 are examples.

Example 2 To 0 parts of vinyl chloride resin [Geonl 03 Ep] I O, 2.7 parts of dibutyltin maleinate polymer and [Table 2
A mixture of the additives shown in ] was formed into a sheet in the same manner as in Example 1, and after pressing, it was pasted on an exposure stand and sampled after 3 years to observe the state of discoloration. Evaluation is based on Example 1
by the same method.

As can be seen from [Table 2], the resin composition of the present invention to which a boric acid ester compound is added has extremely excellent weather resistance.

Similar results were obtained when the known borate esters (A) to (E) of Example 1 were used in place of the tristearylborate ester of Sample No. 4.

[Table-2] Sample Nos. 1 to 4 are comparative examples, and Nos. 095 to 8 are examples.

Example 3 Vinyl chloride-vinyl acetate copolymer resin [Geon 10
3El)-8J], 3.0 parts of dibutyltin maleate polymer, and the additives shown in Table 31 were mixed into a sheet in the same manner as in Example 1, and after pressing, the mixture was placed on an exposure stand. Three years after pasting, sampling was conducted and the state of discoloration was observed.

Evaluation was performed using the same method as in Example 1.

[As can be seen from Table 31, the resin composition of the present invention to which a boric acid ester compound is added has extremely excellent weather resistance.

[Table-3] Sample No. 1 to 2 are comparative examples, and Sample No. 3 to 8 are examples.

Similar results were obtained when the boric acid esters (A) to (E) of Example 1 were used in place of the dibutyltin distearate of samples No. 2.

Example 4 Vinyl chloride tree 1e [Geonl 03 Ep] + 00
Parts by weight, Kaneace B-12 [manufactured by Kanebuchi Chemical Co., Ltd.] 5 parts by weight, dibutyltin bis (benzyl maleate)
A mixture of 3.5 parts and the additives shown in [Table 4] was made into a sheet in the same manner as in Example 1, and after pressing, it was pasted on an exposure stand, and after 3 years sampling was conducted to observe the state of discoloration. .

The state of discoloration was evaluated using the following methods a and b.

a: It is yellow.

b=brown.

As can be seen from [Table 4], the resin composition of the present invention to which a boric acid ester compound is added has extremely excellent weather resistance.

Similar results were obtained when the known boric acid esters (A) to (E) of Example 1 were used in place of the dibutyltin dilaurate of Sample No. 3.

[Table-4] Samples No. 1 to 3 are comparative examples, and Samples No. 4 to 8 are examples.

When the boric acid ester compound represented by the general formula (1) and/or (2) of the present invention is added when a halogen-containing resin is stabilized with an organotin maleate compound, a halogen-containing resin composition with excellent weather resistance can be obtained. is obtained.

Patent applicant: Sankyoki Gosei Co., Ltd. Agent: Patent attorney: Issho Kashi
Written amendment to administrative procedures (voluntary) August S 3, 1986, Relationship to the case of the person making the amendment Patent applicant Address 788 Kuji, Takatsu-ku, Yozaki City, Kanagawa Prefecture Name
Sankyoki Gosei Co., Ltd. Representative Director Seita Furukawa Department 4, Agent 140 Address 1-2-58 Hiromachi, Tokyo Parts Industry Ward (1) “R4” on page 4, line 8 of the specification Corrected to "R4".

(2) Example 1 on page 24, line 1+ to Example 4 on page 31, line 4 are corrected as follows.

[Example 1 Vinyl chloride resin [Geon103 manufactured by Nippon Zeon Co., Ltd.]
A mixture of EpH001, 2.7 parts of dibutyltin bis(butyl maleate), and the additives shown in [Table 1] was kneaded using an 8-inch test roll at 170°C for 5 minutes to give a thickness of 0. 51 sheets were made. 1 Konosheet
00 Kg/cm'' at 150° C. for 10 minutes, and then cut into a size of 30 ma x 100 I to produce four sheets.

Each of the obtained sheets was pasted on an exposure stand facing south with an inclination angle of 45°C. Samples of the pasted sheets were taken 2 and 3 years later to observe and evaluate the state of discoloration.

The state of discoloration was evaluated using the following criteria A, B, and C.

The hem has not changed color at all.

B: Whitening.

C: It has become brown.

As can be seen from [Table 1], the resin composition of the present invention to which a boric acid ester compound is added has extremely excellent weather resistance.

Similar results were obtained when other known boric acid esters, such as the following compounds, were used in place of the tristearylboric acid ester of sample N004.

(R=n-butyl, lauryl, except stearyl (C)), cyclohexyl and oleyl, ethylene glycol, and methoxybutanol) (R°=butylenyl, R”
=stearyl) [Table 1] Sample Nos. 1 to 4 are comparative examples. No. 5 to 9 are examples.

Example 2 A mixture of 00 parts of vinyl chloride resin [Geonl O3EpH, 2.7 parts of dibutyltin maleate polymer, and the additives shown in [Table 2] was formed into a sheet in the same manner as in Example 1, and after pressing, After 2 and 3 years of pasting it on an exposure table, sampling was performed and the state of discoloration was observed. Evaluation was performed using the same method as in Example 1.

As can be seen from [Table 2], the resin composition of the present invention to which a boric acid ester compound is added has extremely excellent weather resistance.

Similar results were obtained when the known borate esters (A) to (E) of Example 1 were used in place of the tristearylborate esters of Samples No. 4.

[Table-2] Sample Nos. 1 to 4 are comparative examples, and Nos. 005 to 8 are examples.

Example 3 Vinyl chloride-vinyl acetate copolymer resin [Geonlo 3
Ep-8J] 100 parts by weight, 3.0 parts of dibutyltin maleate polymer, and the additives shown in [Table 3] were mixed into a sheet in the same manner as in Example 1, and after pressing,
After 2 and 3 years of pasting it on an exposure table, sampling was performed and the state of discoloration was observed. Evaluation was performed using the same method as in Example I.

As can be seen from [Table 3], the resin composition of the present invention to which a boric acid ester compound is added has extremely excellent weather resistance.

Sample Nos. 1-2 are comparative examples, and Nos. 003-8 are examples.

In place of dibutyltin distearate of sample No. 2,
Similar results were obtained even when the boric acid esters (A) to (E) of Example 1 were used.

Example 4 3.5 parts by weight of dibutyltin bis(benzyl maleate) was added to 0 parts by weight of vinyl chloride resin [Geonl 03 EpHO, 5 parts by weight of Kane Ace B-12 [manufactured by Kanebuchi Chemical Industry Co., Ltd.]
A mixture of the additives shown in [Table 4] was formed into a sheet in the same manner as in Example 1, and after pressing, it was pasted on an exposure table, and samples were taken after six months, one year, and two years to check for discoloration. Observed.

The state of discoloration was evaluated using the following criteria a, b, and c.

a: Almost no discoloration.

b: Yellow.

C: It has become brown.

[As seen from Table 43, it can be seen that the resin composition of the present invention to which a boric acid ester compound is added has extremely excellent weather resistance.

Similar results were obtained when the known boric acid esters (A) to (E) of Example 1 were used in place of the dibutyltin dilaurate of Sample No. 3.

Samples No. 1 to 3 are comparative examples, and Samples No. 4 to 8 are examples.

When a halogen-containing resin is stabilized with an organotin maleate compound, adding a boric acid ester compound represented by the general formula (1) and/or (2) of the present invention can improve the halogen-containing resin with excellent weather resistance. (3) The “Scope of Claims” column is corrected as follows.

"1. When stabilizing a halogen-containing resin with an organotin maleate compound, , an aralkyl group, an aryl group, and a cycloalkyl group, R5 is a residue obtained by removing two hydroxyl groups from a polyhydric alcohol having 2 to 6 hydroxyl groups, R
', R'', Rko, -&4 may be the same or different.

X and Y are residues obtained by removing one hydrogen atom from two different carbon atoms of an alkane having 2 to 10 carbon atoms, m.

n represents an integer of 1 or more. ) A halogen-containing resin composition having excellent weather resistance, characterized in that it contains at least one boric acid ester compound represented by the following. ” Procedural amendment (voluntary) 1. Indication of the case 1985 Patent Application No. 147402
No. 2, Name of the invention Halogen-containing resin composition with excellent weather resistance 3. Relationship with the amended person's case Patent applicant address 788 Kuji, Takatsu-ku, Yozaki City, Kanagawa Prefecture Name
Sankyoki Gosei Co., Ltd. Representative Director Seita Furukawa Department 4, Agent 140 Address 1-2-58 (1) Hiromachi, Honbunagawa-ku, Tokyo
Page 21, line 3 of the specification (and above)

Claims (1)

[Claims] 1. When stabilizing a halogen-containing resin with an organotin maleate compound, the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and/or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ( In the formula, R^1, R^2, R^3, R^4 have a carbon number of 1
~30 alkyl groups, alkenyl groups, aralkyl groups, aryl groups and cycloalkyl groups, R^5 is hydroxyl group 2~
Residues obtained by removing two hydroxyl groups from a polyhydric alcohol having six hydroxyl groups, R^1, R^2, R^3, and R_4, may be the same or different. X and Y are residues obtained by removing one hydrogen atom from two different carbon atoms of an alkane having 2 to 10 carbon atoms, and m and n are integers of 1 or more. ) A halogen-containing resin composition having excellent weather resistance, characterized in that it contains at least one boric acid ester compound represented by the following.