DE2115799C3 - Process for improving the strength properties of glass fiber reinforced vinyl chloride homo and copoly mensates and their chlorination products - Google Patents

Description

is constructed.

The reinforcement of vinyl chloride homo- and copolymers and their chlorination products, here briefly referred to as VC thermoplastics, with a wide variety of fiberglass materials is known. in the in general, one achieves with fiberglass materials such as fiberglass fleeces, fiberglass fabrics and fiberglass fabrics Reinforcements, which result in a significant increase in flexural strength, tensile strength, modulus of elasticity, notched impact strength and heat resistance of the VC thermoplastics. Good increases the mechanical property values, however, have so far only been possible if very special processing conditions are observed of the VC thermoplastic with the commercially available fiberglass materials, d. H. taking into account special manufacturing regulations for Laminates. According to the state of the art, an improvement in the gain or Increasing the strength of such laminates is only possible to a very limited extent, for example by the Structure of the glass fiber material and the glass fiber content of the laminate by increasing the pressure:

and the pressing temperature as well as by such glass fiber nonwovens and fabrics, which with one of the known Plastic layers or adhesives, in particular with chromium methacrylate complex compounds or

Silane coupling agents such as j'-aminopropyltri-ethoxysilane, y-Glycidyi-oxypropyl-trimethoxysilane 'or Meth'acrylüxypropyl-trimethoxysilane. were equipped.

Further possibilities for reinforcement \ on laminates, however, in particular to improve the bond between VC thermoplastics and glass fibers not known.

The object of the invention specified in claim 1 is now to provide the reinforcements on VC thermoplastics to be further improved by fiberglass materials and to simplify the laminate manufacturing conditions.

From the large number of VC-Mischpo'.ymerisater surprisingly have the * carboxy group-containing VC copolymers are excellent Adhesion improver especially proven for the interface between VC thermoplastics and glass fiber.

VC copolymers as specified in claim 3 are particularly suitable for such binder layers are.

Further suitable mixtures are given in claims 4 and 5.

Preference is given to 1 to 2 mole percent of those containing carboxyl groups Compound used in the copolymer.

The monounsaturated mono-, di- or tricarboxylic acids contained in the VC copolymers can have an unlimited chain length. Carboxylic acids with 3 to 6 carbon atoms are preferred, such as. z. B. acrylic acid, methacrylic acid, vinyl acetic acid, Crotonic acid, fumaric acid, maleic acid, itaconic acid and aconitic acid. As alkyl and acidic partial alkyl esters and neutral esters, those of the acids mentioned are also preferred. The alkyl part esters should Contain at least one free carboxyl group, but can also in the case of the tricarboxylic acids carry two free carboxyl groups. The alcohol residues of the alkyl esters and partial alkyl esters are said to be more saturated be of aliphatic alcohols of per se unlimited chain length, but such alcohol residues are of 1 to 20 carbon atoms are expedient, those with 1 to 12 carbon atoms are preferred.

The vinyl compounds contained in the VC copolymers should either be vinyl chloride or mixtures of predominantly vinyl chloride and other vinyl compounds such as vinyl acetate.

Vinyl chloride homopolymers can be used to produce the laminates, regardless of the method of production and their properties. Copolymers of vinyl chloride with other olefinically unsaturated monomers can also be used. Further, the "hlorierungsprodukte of said polymers, particularly chlorinated PVC, regardless of its range from about 57 to about 73 ° / ₀ lying chlorine content is usable.

The binder layers made from the above-mentioned carboxyl-containing VC copolymers are most effective as adhesion promoters for VC thermoplastics on glass fibers when their layer thicknesses are in the range from 20 to 500, especially from 40 to 250 millimicrons. Stronger binder layers surprisingly worsen this effect. These binder layers can be prepared by wet impregnation either with a solution in organic solvents or with an aqueous dispersion of the carboxyl group-containing VC copolymer. For such wet impregnation it is advantageous for the purpose of more complete surface wetting of the elementary glass fibers in the nonwoven and fabric threads, but not necessary, to carry out the impregnation in a vacuum or partial vacuum. The solutions or dispersions used for wet impregnation can, based on the VC copolymer, 2 to 3 ° ₀ for a VC-polymers conventional heat stabilizer are lugesetzt. Suitable known surfactants can be added in order to increase the wettability of the glass fibers.
As glass fiber materials for such wet impregnations to reinforce VC thermoplastics, the commercially available glass fiber nonwovens and fabrics as well as the glass fiber fabrics, ultimately also 5 to 25 mm long cut fiberglass, can be used. The glass fiber material can be used in the desized

<5 stand or be equipped with a finish. The previous finishing of the fiberglass material plays a role in the degree of the reinforcement effect of the binder course not a crucial role. The chrome methacrylate already applied by the manufacturer or Silane finish generally does not provide any significant improvement in reinforcement over a single one Fiberglass finishing with a binder layer according to the present invention. One before The Siian finish applied in many cases makes the fibers water-resistant and can thus form the bond with the Improve VC thermoplastics in the event of water exposure and keep them stable.

An additional chemical anchoring of the carboxyl group-containing VC copolymers due to functional groups already on the glass fiber surface adhesive silane finishes, such as B. aminopropylsilane, increases the durability of the adhesion the binder course according to the invention and the strength values do not. Is already from the Fabric manufacture a silane finish of aminopropyl silane on the glass fiber surface, the amount of binder to be applied can be adjusted accordingly can be reduced without a substantial loss of gain increase. this applies for the low application quantities for the approximately 80 to 100 millimicron thick binder layers, which are generally completely sufficient to achieve the optimal gain increases in VC thermoplastics according to to achieve the present invention.

The application of the binder layer of carboxyl group-containing VC copolymers to the glass fiber material can take place at any time before the actual processing, ie pressing to form the multilayer laminate. This binder layer can be applied to the glass fiber material before, during or after the manufacture of the nonwoven or fabric, i.e. also at the time of the application of the finish. These carboxyl group-containing VC copolymers can be used directly by the manufacturer of glass fiber materials in the same way as special equipment that is to be used specifically for the reinforcement of VC thermoplastics.

The amount of the vinyl chloride copolymers used as the binder may be from 0.1 up to 12 ° / _0, preferably 0.3 to lO ° / o. based on the weight of the fiberglass materials.

The laminates can be pressed in the thermoplastic area of thermoplastics, e.g. B.

at 189-210 ⁰ C and pressures of 10 to 150 kp / cm ^2, but also different pressing conditions are possible. Glass fiber contents of 10 to 70%, based on the weight of the laminates, are possible.

In the examples below, 2 minutes became 200 ° C. under slight pressure

For the sake of comparability, the material is heated together and then at 50 kp / cm ² in 4 minutes

Settlements, glass fiber content, the structures of the laminate pressed.

The 13 rigid PVC films have a total weight temperature chosen so that the effect of the binder 5 of 182 g, so that the finished laminate has a glass layer expressed in number. Has a rock fiber content of 30%,
Gerte effect of the binder layer under optimal pressing conditions, z. B. at high and then also complex pressing pressures, the example shows 16 B eis ρ ie 1 2

The results of the exemplary embodiments are in io (comparative example)

Table I compiled. The measured values show ^e

clearly through the binder layer of carboxy! - In the same way as in Example 1,

group-containing VC copolymers produced a laminate with the same structure,

fene additional, considerable increase in gain in which, however, the heat-

and on the other hand the dependency of the reinforcement 15 desized glass silk fabric without the addition of a

increase of the application quantity or layer thickness of the binder is used,
this binder course. So are z. B. additional increases in strength properties by 50 to 100%

for flexural strength (DIN 53452) and also by 25 B e 1 s ρ 1 e 1 3
up to 40% with tensile strength (DIN 53'.55) L-module 20 (verification with <niel)
(DIN 53452) and U-notched impact strength (DlN 53453) ^K vergieicru.Dei.piei;
been received. As in Example 1, a laminate still built in the same way according to Vi cat (DIN 53453) under the same conditions is increased by about a further 10 ° C show that even with a desized fiberglass fabric with 0.8% y-amino applied amount of 2% of the glass propyl-triethoxy-silane fiber material before pressing, optimal increases were achieved,
however, with higher amounts of binder, example 4 has so far been used technically for glass fiber reinforced VC thermoplastics
Strength values not achieved can be achieved. 30 (comparison example)

When using binder courses according to the ν & ν ι

Invention can preheat the fiberglass For further comparison is without use

materia.ien in a separate operation are not required. an insert made of glass fibers from the in Example 1

According to the present invention, an essential PVC becomes one under the same pressing conditions

Liehe improvement of the bond or the adhesion 35 4 mm thick press plate produced,
between the VC thermoplastic and the glass fiber surface.

Example 5

The production of the laminate is carried out as in Example 1, with the only difference that the

For the production of a 4 mm thick laminate in Example 1, a binder made of rigid PVC (suspension polymer K value 60) layer of 83 millimicrons, corresponding to a layer of glass silk fabric in a plain weave with 45 layers of 2.0% of the fabric weight, A basis weight of 160 g / m ^{2 is} used, what is applied by wet impregnation warp and weft threads from Ε-glass silk from the transverse of the twelve 78 p, heavy pieces of glass silk fabric with section 9 microns and the titer 680 dte.x 30 g a 5.2% solution of MP-A in butanone. This glass silk fabric is achieved by heating,
desizing, so that the original sizing is ent- co

is distant. For a 4 mm laminate, there are now 12 glass B bis η ie 1 6
pieces of silk fabric 200 x 200 mm with a total weight of 78 g by means of wet impregnation under vacuum with 0.5% of a carboxyl group. Copolymer as 13% vinyl acetate. 1% maleic acid (in the following briefly applied binder layer, called MP-A by wet impregnation) coated as binder layer. Corresponding to 40 g of a 9.7% solution of MP-A in butanone corresponding to the absorbency of this glass silk fabric and which corresponds to a layer thickness of around and the viscosity of the polymer solution required 415 millimicrons,
for this purpose 25 g of a 1.56% solution of the mixing 60
Polymer in butanone, which is used as a stabilizer 3%

Di-n-butyltin-bis-thioglycolic acid isooctyl ester, Example 7
are set. This order quantity corresponds to one
Binder layer thickness of around 20 millimicrons.

The 12 glass sheets pretreated and dried in this way are 65 The manufacture of the laminate is carried out as in

pieces of silk weave are alternated with 13 hard play 6, the only difference being that a binder

PVC foils 200 x 200 x 0.25 mm, a layer of 10% MP-A on top of one another, applied to the fabric

tet and the stack thus obtained in the press is inside.

Example 8
(Comparative example)

The production of the 4 mm thick laminate of 200 × 200 mm is carried out in the same way as in Example I. To build up the laminate, however, eight layers of glass silk fabric weighing a total of 80 g with a surface weight of 260 g / m ² made of 10 micron thick Ε-glass fibers made of 680 dtexin plain weave are used, which is a thread size of about 0.8 that is customary in industrial production % wear a mixed route of polyvinyl alcohol and aminopropylsilane. Also nine 0.4 mm thick hard PVC Folicn with a total weight of 190 g are needed for this laminate to form a laminate with 30 ° to obtain / ₀ glass fiber content. For laminate 5a, the glass fiber fabric GIs 3205 is used in its original, non-pretreated condition.

Example 9

Example 8 is repeated, but the glass silk fabric mentioned there additionally with a binder layer of the copolymer A coated, which makes up 2.1% of the weight of the glass silk fabric and a layer thickness of 97 millimicrons. This binder layer is wet impregnated with 32 g of a 5.25% solution of MP-A in butanone obtained *

Be is ρ ie I 10
(Comparative example)

A laminate is produced according to Example 8, but with a glass fiber content of 20% having. For this purpose, five pieces of glass silk fabric, weighing a total of 50 g, of those mentioned in Example 8 are used Art and six 0.6 mm thick rigid PVC foils are used.

Example 11

Example 10 is repeated, but the above-mentioned glass silk fabric is previously additionally treated with 2.0% of the copolymer A coated as a binder layer, the weight of which has a layer thickness of 92 millimicrons is equivalent to. The compression is carried out at 200 ° C. under 12 kp / cm * in 3 minutes.

Example 12

According to Example 1, a laminate with 30% glass fiber content is produced. The finished laminate is made made of 12 layers (78 g) pieces of glass fiber fabric and 13 layers of 0.25 mm thick PVC film.

The glass cloth according to Example 1 is coated before the! ^ Amination with 5 ° / ₀ of a copolymer as a binder layer, which is composed of 95% vinyl chloride and 5% Maleinsäuremonocetylester. This coating is achieved with 44 g of an 8.9% solution of MP-B in tetrahydrofuran.

Example 13

Example 6 is repeated, but instead of the binder layer made of MP-A, a binder layer is made

a) 4.0 ° / ₀ of a copolymer of 97% vinyl chloride and 3.0% acrylic acid,

b) 5.5% of a copolymer of 97% vinyl chloride and 3.0% methacrylic acid,

c) 4.5% of a copolymer of 96.5% vinyl | chloride, 2.5% methacrylic acid and 1.0% methyl methacrylate used'.

The strength properties correspond to those given for Example 6 in the table.

Example 14

Example 12 is repeated in a corresponding manner, but instead of MP-B a binder course

a) 4% of a copolymer of 96% vinyl chloride and 4% fumaric acid monoethyl ester,

b) 4% of a copolymer of 95.5% vinyl chloride and 4.5% fvialeinic acid riono-i-biityl ester,

c) 4.8% of a copolymer of 97% vinyl chloride and 3% maleic acid,

d) 4.5% of a copolymer of 95% vinyl chloride and 5% aconitic acid,

e) 7% of a copolymer of 87% vinyl chloride, 10% vinyl acetate and 3% methacrylic acid,

f) 7% of a copolymer of 89% vinyl chloride, 8% vinyl acetate and 3% maleic acid monomethyl ester

has been used. The strengths determined correspond to those given in the table for example 12.

Example 15

Betspiel 11 is repeated, but instead of the rigid PVC sheets, those made of chlorinated PVC with a K value of 60 or 68 were used, which contained a] 62% Cl and b) 67% Cl. The FestigkeilswerU correspond to those given for Example 11 in the table; the Vicat values were, however, with a K value of 60 a) 111 ° C and b) 124 ° C, with a K value of 6! a) 115 and b) 140, compared with Vicat values, without glass fiber reinforcement, which are each about 15 C deep.

Example 16

Example 1 is repeated under the conditions given there, but the press pressure 150kp / cm *. The strength values are against Improved further above that given in the table, with the increase in flexural strength being particularly important at 172Okp / cm * and the Vicat at 100 "C

9 10

Table of structure and mechanical property values of laminates in the exemplary embodiments

example

PVC (S 60)

Glass fiber fabric, type no

Glass fiber content. %

Binder course

Plain / finish

Flexural Strength, kp / cm ^a

Tensile strength, kp / cm ²

E-module · 10 ³ , kp / cm ²

Impact strength, cmkp / cm ²

U-notch impact strength, cm · kp / cm ² heat resistance, Vicat, ° C

(in glycol)

92105
30th

0.5% MP-A
without
1580
1480
120
49

42
94

92105 30

without

without

1030

1300

101

36 85

92015
30th

without

/ 0.8 V _n S

1360

1410

112

44

43
93

without

without

without

without

830

600

31

> 160 (ng)

2.8

73

92105 30

2.0% MP-A without 1801 1550 127 50

48 94

92105 30

5% MP-A

without

1980

1600

131

60

54 95

example

10

12th

Glass fiber fabric, type no

Glass fiber content,%

Binder course

Plain / finish

Flexural Strength, kp / cm ¹

Tensile strength, kp / cm ²

Modulus of elasticity ■ 10 ³ , kp / cm ²

Impact strength, cmkp / cm ²

U-notch impact strength, cm ■ kp / cm ² Heat resistance, Vicat, ° C

(in glycol)

ng = not broken.

92105
30th

10 ° / ₀ Ml'-A

without

1890

1750

130

60

60

95

GIs 3205

without

PVA / Sil.

1460

1420

102

94

GIs 3205
30th

10 / .ΜΡ.Λ

—Ϊ »/ U - -

PVA / Sil.

1800

1640

126

87

79

94

GIs 3205

20th

without

PVA / Sil.

1270

1320

66

86

65

82

GIs 3205

20th

2.0% MP-A PVÄ / Sil. '1560 1440 74 87 68

83

92105 30

5% MP-E

without

1440

1460

119

45

45

Claims (9)

Patent claims: 1. Process for improving the firmness properties of glass fiber reinforced vinyl chloride homo- and copolymers as well as their chlorination products, characterized in that the fibers of the Glasfaserrr.materials before Incorporation into the vinyl chloride thermoplastic with a binder layer of a carboxyl group Vinyl chloride copolymers are coated. 2. The method according to claim i. characterized, that the binder layer thickness of the coating of the carboxyl group-containing vinyl chlorine: d copolymers on the glass fibers in the range from 20 to 500, preferably between 40 and 250 millimicrons. 3. Process according to claims 1 and 2, characterized in that a carboxyl-containing vinyl chloride copolymer is used for the binder layer, which consists of 75 to 99.5 ⁰ Z _{0 of} a vinyl compound and 0.5 ° ₀ to 25 ° _{0 of} a monounsaturated aliphatic mono-, di- or tricarboxylic acid and / or their partial acidic alkyl esters and / or their neutral alkyl esters. 4. The method according to claims 1 to 3, characterized in that a carboxyl-containing vinyl chloride mixed pole for the binder layer; merisate is used, which is composed of 92 to 99.5 ⁰ Z ₀ vinyl compounds and 0.5 to 8 °, _{0 of} a monounsaturated aliphatic mono-, di- or tricarboxylic acid or their partial alkyl esters, the proportion of vinyl compounds from 5 to 20 ° ₀ vinyl acetate, based on the vinyl chloride copolymer, and the remainder of the Vinylve bonds consists of vinyl chloride. 5. The method according to claims 1 bi * 3, characterized in that a carboxyl group-containing vinyl chloride mixture for the binder layer " polymer is used that consists of a) 80 to 95 ° ' _o vinyl chloride and 5 to 20 ° / _{0 of} a neutral alkyl ester of a monounsaturated aliphatic mono-, di- or tricarboxylic acid or b) 90 to 99.5 °; ₀ vinyl chloride and 0.5 to 10 ° / ₀ of a mono-unsaturated aliphatic mono-, di- or tricarboxylic acid or its acidic or Alkylteilestern c) 75 to 94.5 ° ₀ vinyl chloride, at least 5 °; ₀ of a neutral alkyl ester of a mono-unsaturated aliphatic mono-, di- or tricarboxylic acid and at least 0.5 ° / "a monounsaturated aliphatic mono-, di- or tricarboxylic acid or its acid Alkylteilestern, not more than 25 ° / ₀ of the total amount of the monounsaturated aliphatic mono-, di- or tricarboxylic acid and / or their acidic Alkylteilestern and / or their neutral alkyl esters, with the proviso that 20% of a neutral alkyl ester of a mono-unsaturated aliphatic mono-, di- or tricarboxylic acid or 10 ° / ₀ of a simple unsaturated aliphatic mono-, di- or tricarboxylic acid or their partial acidic alkyl esters is not exceeded, 6. The method according to claims I to .5, characterized in that the carboxyl-containing vinyl chloride copolymer with the addition of 2 to 3 ⁰ Z _{0 of} a conventional heat stabilizer in the form of a solution in organic solvents or in the form of an aqueous dispersion on the binder layer Ways of wet impregnation is applied to the fiberglass material. 7. The method according to claims 1 to 6, characterized in that the glass fiber material either in the desized state or with a finish consisting of a known hrom methacrylate complex or a subs \ uated alkyl trialkoxysihr such as B. γ-aminopropyl-triethoxysilane, γ-glycidyloxypropyl-trimethoxysilane or methacryl-oxypropyl-trimethoxysilane consists. 8. The method according to claims 1 to 7, characterized in that the glass fiber material in the form of fiberglass fabrics, fiberglass fabrics, fiberglass mats or fleeces or loose 5 to 25 mm long glass staple fibers are used. 9. The method according to claims 1 to 8, characterized in that the coated with a binder layer, previously desized or finished glass fiber material miteinerr vinyl chloride homo- or copolymer as a matrix under suitable processing conditions in the thermoplastic range of this thermoplastic at temperatures around 180 to 210 C and Depending on the composition and structure of the glass fiber-thermoplastic mixture, pressed to form the laminate ^{at pressures of 10 to 150 kp / cm 2 b;: w.} is processed.