DE1569014A1 - Resin-like molding and coating compound that is heat and light stable - Google Patents

Description

The invention relates to stabilizers for vinyl halide resins and to resinous molds containing them Coating compounds.

During their processing into plastic sheets or webs, rigid or rigid bodies and other objects vinyl halide resins are usually subjected to elevated temperatures. The resins treated in this way tend to Decomposition to such an extent as to induce discoloration. This decomposition is particularly pronounced if rejects or scrap parts of the resins are again in an apparatus operated at elevated temperatures. are processed. Even if the decomposition or the

0 0 9 8 I S / 1 8 2 3

ORIGINAL INSPECTED

1569QU

- 2 - - - -

construction does not cause any noticeable reduction in the physical properties of the resins when heated, v. ^T ird their Anv / endbarkeit or their use limited by the Verf2rbun <*. There is a need in the art for stabilized vinyl halide resin compositions which can withstand the heating to which they may be subjected during and after processing without darkening or other deterioration.

It is to have a good stability of arms and light it is desired that the vinyl halide resin compositions have a light color Color and that it retained its light color when heated

It is already known that vinyl halide resin compositions provided with asbestos as a filler have a negative effect on the deterioration caused by heating or the deterioration brought about by it Degradation can be stabilized or made resistant by giving them certain nitrogen containing compounds incorporated, which in their structural formulas the group

= N-C-N =

Il

N
ι

contain. Albeit such compositions or hates Having a relatively light color, they are still inorganic for many technical uses Vinyl halide resins containing filler, e.g., asbestos

009815/1823

BATH ORIGINAL

15690H

too dark, such applications; areas include e.g. white or light colored floor coverings. The color retention of such known resins are also in need of improvement for applications of this kind.

The term "nitrogen-containing compound" as used herein refers to nitrogen-containing only Compounds, plural marriage in their structural formulas the group

= N-C-H =

ti

N
ι

contain. .

According to the invention, a heat- and light-stable resinous mass contains which is a vinyl halide resin comprises an inorganic filler and a nitrogen-containing compound as mentioned above and further an anhydride of a polycarboxylic acid.

The nitrogen-containing compounds used by the haters according to the invention can in their formulas comprise an s-triazine ring, in which case they have the formula

. NH-C C-WHR.

¹ I. Il ¹

N N

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BATH ORIGINAL

- -If -

have, in which R. in each case a hydrogen atom, one Phenyl group, an alkyl group with 1 to 5 carbon atoms or a carbon atom in an s-triazinine p and 1 * 2 an amino group, a substituted amino group, e.g. Alkylamino or phenylamino group, or a phenyl group. On the other hand, the nitrogen containing Compounds of acyclic compounds of the general formula below

R ₀ IiK - C - IfIIR ₀

O κ Ο

NH

consist, in which R "a hydrogen atom, a phenyl group, represents a cyano group or an alkyl group having 1 to 5 carbon atoms. Examples of the practical Execution of the invention? applicable nitrogen The compounds containing melamine, lower alkyl melamines, e.g. methyl melamine and propyl melamine, phenyl melamine Kelam, Miere, Benzoguanamine, Guanidine, Dicyandiamide And Melanilin. Salts of the above compounds, e.g., the carbonate, hydrochloride and sulfate salts can also be used. In the stabilized vinyl halide compositions may be a single nitrogen-containing compound or one or more of these compounds to be available. Preferred nitrogen-containing compounds

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BATH ORIGINAL

T5690H

fertilizers are melamine, dicyandiamine, benzoguanamine and mixtures of it, as they are masses with particularly bright colors and good color retention.

A wide variety of polycarboxylic anhydrides can be used in the novel stabilizers in combination with the nitrogen-containing compounds noted above. These include anhydrides of saturated and olefinically unsaturated aliphatic polycarboxylic acids, and anhydrides of aromatic and cycloaliphatic polycarboxylic acids. The polycarboxylic acids from which the anhydride is derived, can be 2, 3 or ^l l · carboxyl groups. In most cases the use of anhydrides of dicarboxylic acids is preferred. Examples of useful acid anhydrides include: succinic anhydride, glutaric anhydride, adipic anhydride, Doecenylbernsteinsäureanhydrid, citraconic anhydride, itaconic anhydride, maleic anhydride, chloromaleic anhydride, bromomaleic anhydride, TricarballjL-anhydride, phthalic anhydride, chlorophthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3,4-dimethyl ~ 6-isobutenyltetrahydrophthalsäureanhydrid, Hexachloroendomethylentetrahydrophthalsäureanhydrid, Trimellitic anhydride, pyromellitic anhydride and maleic anhydride addition products of cyclopentadiene, methylcyclopentadiene and other unsaturated hydrocarbons.

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BATH ORIGINAL

15690H

A preferred anhydride of a polybasic carboxylic acid is Dodeceny / succinic anhydride.

The stabilizer compositions according to the invention generally contain about 0.1 part to 3 parts by weight of the acid anhydride per part by weight of the nitrogen-containing compound.

A further improvement in the original coloration and color retention of the vinyl halide resin composition can often be done by using a multi-valued. Alcohol with four or more hydroxyl groups in combination with the nitrogen-containing compound and the acid anhydride. Among the polyhydric alcohols, which Can be used are pentaerythritol, dipentaerythritol, sorbitrile mannitol and methyl glucoside, also The polymeric alcohols of the general formula can be used

CH _n -

- CH - CIL

CH ₂ OH

in which η is a number in the range from 5 to 10. One such polymeric alcohol which has a molecular weight of about 1150 is commercially available under the

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BATH ORIGINAL

Trademark Resinous Polyol X-150 (Shell-Chemical Co.) available » The amount of polyhydric alcohol used can be varied within wide limits, wherein about 0.3 to 2 parts by weight of the polyhydric alcohol usually to a Cew »part of the nitrogen-containing compound uses x ^ earth.

Only a small amount of the new stabilizing agent according to the invention needs in the vinyl halide masses ^ emäP; of the invention to be present su. It has been found that as little as 0.5 part by weight of the stabilizing agent per 100 parts by weight of the vinyl halide resin leads to a noticeable improvement in the temperature and light resistance. About 10 parts by weight or more of stabilizing agent can be used, but these larger amounts do not bring about any further improvement in the properties of the shark-like cash register and are therefore usually not used. Although the amount of Rtabilisierungsmittels which provides an optimal VJärine- and light stability, qsmittelkomponenten upon such factors as the choice of the stabili _t and the selection of Vinylhaloq; enidharzes depends, is usually an amount of 1 to 5 parts by weight of the stabili ^ sittel used per 100 parts by weight of vinyl halide tenide resin.

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BATH ORIGINAL

The vinyl halide polymers which can be used in the compositions according to the invention are those by polymerizing a vinyl halide in the presence or the absence of any other polymerizable compound. The one used here The term "vinyl halide resin" includes vinyl halide homopolymers, e.g. polyvinyl chloride and polyvinyl bromide, as well as copolymers, e.g. those produced by the implementation of a Vinyl halide with at least one other polymerizing

P baren monoolefin, for example vinyl acetate, vinyl propionate, vinyl butyrate, vinylidene chloride, styrene, Ilethyl methacrylate, dialkyl fumarate or maleate or the like. Copolymers formed * Chloride is usually used as the vinyl halide, although bromide and fluoride can also be used. The copolymers which can be used in practicing the invention are those made from at least 70% vinyl halide and up to 30 % of the other polymerizable monoolefinic compound. "'...

Although the stabilizers according to the invention in vinyl halide resins, which include a wide variety of inorganic Contain fillers, 'can be used, • are & ie in particular in asbestos as filler ε tof.§. containing

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BATH ORIGINAL

Vinyl halide compositions, for example those used in. are used in the manufacture of floor coverings, valuable. Among the inorganic fillers used in the masses according to the invention may be present both fibrous and non-fibrous fillers are useful. Although each type of filler is the only one inorganic filler can be used contain the masses generally both fibrous and fibrous non-fibrous fillers.

The fibrous fillers found in the new vinyl halide resin compositions may be present according to the invention include asbestos and rock wool (mineral wool). Asbestos is the most commonly used and preferred fibrous filler. Usually it is in an amount of about 50 parts to 200 parts, and preferably 80 parts to 150 parts per 100 parts by weight of the vinyl halide resin available "Any asbestos that technically receives- ' lent qualities »those in the manufacture of flooring compounds uses' wepdjsft »& ann at des Execution of the BjM: indufcg suk »application

Suitable non-fibrous anoganic fillers encompass many of the brewed ugles as fillings in the material used in art. Examples of this are calcium carbonate,
bonat _t

^> * "Λ ^J " ^Ä ii ^r

v-

..- ■■■. - αο -

Fuller's earths and magnesium silicate »and pigments, e.g. Titanium dioxide, iron oxide and lead chromate. The non-fibrous fillers x ^ earth generally in amounts in the range of 50 parts to 300 parts, and preferably from 100 parts to 200 parts per 100 parts by weight of the vinyl halide resin used. Although a single non-fibrous filler can be used, · is mostly a mixture of two or more of these fillers, which at least a pigment includes used.

Any of the common plasticizers for vinyl halide resins can be used in the compositions of the invention. These include, for example, di-2-ethylhexyl phthalate, dibutyl sebacate, tricresyl phosphate or the like. The amount of plasticizer used is generally in the range of about 5 to 100 parts by weight per 100 parts by weight of the vinyl halide resin, "with 15 parts to 50 parts being preferred.

In addition to the constituents indicated above, the vinyl halide resin compositions can also contain one or more of the low and light stabilizing agents known in the art for vinyl halide resin compositions. This u-mfassen as metal soaps, such as barium, cadmium and zinc salts of fatty acids _t benzoic acid or "p-tert, -ButylbenzoesÄure, metal phenates as the barium _t cadmium and zinc salt" won phenol or an alky! Phenol, organic Phos phite, for example, triphenyl phosphite, diphenyl octyl phosphite and

'·; ■., -; 009815/1823 _;

J t ■ ·· '? ■ i ".-

IsooQ-tyl-di-tert.i-octyiphenylphosphite, 'and epoxidized oils, e.g. epoxidized soybean oil and esters of epoxidized Tall oil fatty acids. Extenders, resins, solvents, dyes or the like. can also be used in the usual quantities used for the purposes indicated must be available.

The stabilizing agents according to the invention can the vinyl halide resin compositions by any convenient one Procedures are incorporated. For example, the -. Components of the stabilizers the vinyl halide resin compositions separately or as a mixture of the components of Stabilizing agent, possibly with a content an inert diluent, ζ. B. calcium carbonate

. or an organic solvent, are added, The vinyl halide resin, inorganic filler, stabilizer and other ingredients can then be mixed with or without the aid of a volatile solvent be and the mass obtained can be on rollers at a Temperature of approximately 93 ° - 177 ° C (200 ° to 35O ° F) mixed until it is homogeneous. The stabilized resinous mass can then be taken out of the mixer in the form of a film or a web or sheet of the desired thickness can be removed. The product obtained thereby can be removed as such

or can be used after a polishing or embossing treatment «''

00 9 615/18 2 3

The invention is illustrated below by way of examples explains in more detail in which the specified parts and percentages are based on weight, unless otherwise is specified.

example 1

A mixture of 100 parts of a copolymer of 80% vinyl chloride and 20% vinyl acetate, 100 parts Chrysotile asbestos, 160 parts of granular calcium carbonate,

2.25 parts by weight of a stabilizer were added to 18 parts of dipropylene glycol dibenzoate, 2.5 parts of epoxidized soybean oil and 12 parts of titanium dioxide (rutile). The mixture was then mixed at room temperature and then put into a mill with rollers driven at different speeds whose Oberflcichentemperatur means V, ⁷ asserdampf at about 150 ⁰ C (300 ⁰ F) was maintained, is introduced. the mixture was for 5 minutes rolled or mixed, and then from the V / alzen in F-ori ;. of a homogeneous sheet or Homogeneous sheet about 1.14 Mn (0.045 inches) thick. To determine its thermal stability, 2.54 χ 2.54 cm (1x1 inch) samples of the masses were placed in a forced air oven at a temperature of about 16 ° C (330 ⁰ F) is introduced and samples are removed from it at regular intervals • until significant degradation or significant

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ORIGINAL BATHROOM

156 9.0: TA

The deterioration had taken place, which was due to a change in color was displayed. The heat stability values of the stabilized compositions are given in Table I below listed. In this table as well as in the following Tables will have a numeric scale to indicate the color of the samples, with a rating of 1 being very Pale gray color, which was caused by asbestos and others Fillers represents the inherent color given to the vinyl halide resin, 2 a bluish-gray, 3 purple-gray, 4 · purple and 5 denote brown color.

For comparison purposes, Table I also includes the heat stability values of compositions which are used as stabilizers contain either melamine or a mixture of melamine and a dicarboxylic acid.

00981571823

Table I.

example
No.

Stabilizing agent

Share Anje 100 fangs-parts colour

Color according to

Number of minutes

at about 16 6 ⁰ C (_33Di

IA

IB

Melamine 1.5

Maleic anhydride 0.75

Melamine 1.5

Phthalic anhydride 0.75

IC melamine 2.25 2 ID melamine 1.5 2 Maleic acid 0.75 IE melamine 1.5 2 Phalic acid 0.75 IF melamine 1.5 2 Fumaric acid 0.75

15 30 45 80 75 90

1 1 1 12 3 5

1 1.1 12 3 5

2 2 2 2 3 3 5 2 2 2 3 3 3 5

2 2 2 2 3 3 5

2 2 2 3 3 3 5

Parts stabilizer per 100 parts vinyl halide resin

From the values listed in Table I it can be seen that
that the compositions containing stabilizing agents according to the invention (Example No. IA and IB) had lighter initial colors and better color retention than the comparison compositions which only contained melamine (Example No. IC) or

009815/1823

Melamine in combination with a dicarboxylic acid (examples No. · ID, IE, and IF).

Example 2

Compositions were prepared using the approach and procedure described in Example 1, with the modification that different amounts of the new statilizing agents according to the invention were added. The thermal stability values of these compounds, which vnn by heating the sample at a temperature about 171 ° C (310 ⁰ F) were obtained are shown .in Table II below. . *

Table II
Parts

100 arrival

Divide catch color by number of

Resin paint minutes at 171 ° C (340 ⁰ F)

At-
s floorboard
Rr. Stabili
sizing
middle 2A melamine
Ph th a Is aur e aiihydr id
.- ■. - 2 B melamine
Phthalic anhydride 2C Dicyandiamide
Phthalic anhydride 2D melamine 2 F, melamine 2F 'Dicyandiamide

10 20 30 10 50 60 70 80 90 IOC 1 111 2 2 2 3 3 3 3 1 1 1 112 2 2 3 3 3 1 111 2 2 3 3 3 5

2 2 2 2 3 _v 3 3 1 5 2 * 2 2 2 3 3 311 5

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BATH ORIGINAL

- 3L6 -

Example 3

A mixture of 100 parts of a copolymer of 80 % vinyl chloride urti 20 % vinyl acetate, 150 parts of chrysotile asbestos, 220 parts of granular calcium carbonate, 14 parts of butyl benzyl phthalate, 14 parts of diisooctyl phthalate, 3.5 parts of epoxidized soybean oil and 50 parts of titanium dioxide (anatase, j) was with one of the stabilizers used according to the invention or with a comparative stabilizer. The mixture was mixed at room temperature and then introduced into a rolling mill with two driven at different speed rolls whose surface temperature was maintained at about 14 9 ° C (300 ⁰ F). The mixture was milled or rolled for 5 minutes and then removed from the rolls in the form of a homogeneous sheet or sheet about 3.04 mm (0.120 inches) thick. The Wämrestabilitst of these compositions which was obtained by heating or ^ of the sample at a temperature of about 177 ° C (35O ⁰ F) determined are listed in Table III below.

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- 1-7 -

Table III

. Parts with- Stabil- each 100 allusion- parts catch- ■ no. Medium resin color

Color by number of minutes at 177 ° C (3SO ⁰ F)

3A melamine 2 1 maleic anhydride 1

3B melamine 2 1 succinic anhydride 1

3C melamine 2 1

Phthalic anhydride 1

3D melamine 2 1 maleic anhydride 1: pentaerythritol 1 ■■■ - .:

3E dicyandiamide 2.2 1 ■ phthalic anhydride 0.2

3F Dicyandiamide
Phthalic acid
anhydride 2.2 1 3G Dicyandiamide
Phthalic acid
anhydride 2.0
0, H 1 3H melamine 3 2. 31 melamine
Maleic acid 2
1 2 3Y melamine
Fumaric acid 2
1 2 3K ' melamine 2 2

5 10 15 20 25 30 40 50. 60

1 1

1 1 1 I.

1 1

1 1

Diglycolic acid 1

1 11 12 3 "3 3 5 11 1 l 1 2 2 2 3 11 12 2 3 3 3 3

2 2 2 2 2 33 3 5 Γ 2 2 2 3 3 3 3 5

2 2 22 2 2 3 3. "" 5

2 2 2 -3 3 3 3 3 3 5 ^:

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Table III (continued)

Parts

At- Stabil- per 100 allusion- parts catch- color according to number of no. Medium resin color minutes at 177 ° C (350 ⁰ F)

5 10 15 20 25 30 40 50 60 70

3L dicyandiamide 3 2 2 22 2 23335

3M melamine 2 2 2 222233335

Pentaerythritol 1

3N pentaerythritol 1 2 234 4 445 maleic anhydride 1

• From the values in Table III it can be seen that the stabilized compositions according to the invention (Examples No. 3A - 3G) had better initial colors and these colors lasted longer than the comparison materials (Examples 3H - 3N) retained.

Example 4

To a mixture of 100 parts of a copolymer of 70% vinyl chloride and 30% vinyl acetate, 125 parts of chrysoiil asbestos, 180 parts of granular calcium carbonate, 40 parts of magnesium silicate, 15 parts of coumarone-indene resin, 30 parts of di-2-ethylhexyl phthalate and 20 parts of titanium dioxide (rutile) were 3% by weight of a stabilizer according to the invention or a comparison "

009815/1823.

Stabilizer added. The mixture was mixed at room temperature and then fed into a mill with two V-rolls driven at different speeds, the surface temperature of which was maintained at about -149 ° C (30O ⁰ F). The mixture was milled or mixed for 5 minutes and then removed in the form of a homogeneous sheet or sheet about 1.5 mm (0.065 inches) thick. The heat stability values of the compositions were determined by heating samples at about 149 ° C (300 ° F) and are listed in Table IV below.

Table IV '

at
game
Wr. Stabili
sizing
middle Parts
100 each
Parts
resin At-
catching
colour 2 2 15th Color according to
Minutes at 45. 60 number
149 ⁰ C from
(300 ⁽ 4th 2 30th 2 2 75 90 105 3 4A Dicyandiamide
Ph tha Is clur eanhy drid 1.5
1.5 1 1 2 1 2 3 3 3 4th 4B Dicyandiamide
■ Phthalic anhydride
Sorbitol HHH 1 3 1 3 3 2 2 3 4th 4C Dicyandiamide 3 3 2 3 2 3 3 4 4th 4 ■■ -. 4D Sorbitol 3 2 2 3 4th 3 4 4th 4E Sorbitol
Phthalic anhydride 1.5
1.5 3 4 4

009815/18 23

Claims (8)

5Ü0H claims 1. Heat and light stable resinous molding and coating compound, which a vinyl halide resin »an inorganic one Filler and a nitrogen-containing compound having a group represented by the formula below Il in its structural formula, characterized in that it comprises an anhydride of a polycarboxylic acid in an amount of contains about 0.1 to 3 parts by weight of the anhydride per part by weight of the nitrogen-containing compound. 2. Mass according to claim 1, characterized in that the anhydride consists of dodecenyl succinic anhydride. 3. Composition according to claim 1 or 2, characterized in that the nitrogen-containing compound of melamine, Dicyandiamide, benzoguanamine, or mixtures of two or more several of the named compounds exist. H. mass according to one of claims 1 to 3, characterized characterized in that the inorganic filler consists of asbestos. 5, Ilasse according to claim 4, characterized in that it contains 50 to 200 parts by weight of asbestos and 0.5 to 10 parts by weight of the sensitizing agent per 100 parts by weight of the vinyl _/ halide resin. 1563014 6, composition according to claim 5, characterized in that it contains 80 to 150 parts by weight of asbestos and 1 to 5 parts by weight of the stabilizing agent 5e ^ & ® parts by weight of the resin. : ■ .. ■ -. \ 7. Composition according to one of claims 1 to 6, characterized in that the polycarboxylic acid consists of a dicarboxylic acid consists. 8. Composition according to Ehern of claims 1 to 7, characterized characterized in that the Po ^ carboxylic anhydride from phthalic acid reanhydride. 9, mass according to one of claims 1 to 8, characterized characterized by having a polyhydric alcohol Contains at least 4 hydroxyl groups, the Ve ^ iiält conditions 0.1 to 3 parts by weight of anhydride and 0.3 to 2 parts by weight of polyhydric alcohol per part by weight of nitrogen-containing compound.