JPS5943200A - Paper sheet with high latex content - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an alternative to impregnated glass webs;
In particular, the fracture strength and delamination resistance (d, olam
, Lnation renlstp-nce).

Surprisingly, it is possible to obtain thermoplastic sheets with excellent mechanical properties directly in one pass on a paper machine.
It has been found that the proportion of latex deposited can be increased to a considerable extent without loss of potency.

In particular, a double flocculation method is used for the production of such sheets.

In this specification, the two-stage flocculation method refers to a method in which a flocculation agent is added before and after the addition of latex.
201. □ (filed in 11. Norance Patent Application No. 7
No. 8-18447, Mei No. 1111, and a person skilled in the art can easily understand the first part of its use.
r-Details can be queried.

Having the composition described below, for example, the product, 2/6 of ton 1+i
A product with an unusual total fax ratio that can reach up to 2 is produced on a paper machine:'! It is worthy of note 1 that it has been recognized that if (15) is true, and it is something to be said about.It has not been considered to be a yōrohi until now.

The new products obtained are characterized by their level of breaking strength, both cold and hot.

Additionally, for example plastisol (pvo powder ten plasticizer)
Use 2 pieces of food, then make about 160 yen.
After heat treatment at ~200°C, it is very difficult to delaminate the resulting hybrid product.

Furthermore, the obtained product has good flexibility.

As a result, the product according to the invention may be used as a replacement product for impregnated glass webs, especially those used in floor coatings and wall coatings.

In the implementation of nonexplosion ψ, the choice of latex has a range of properties such as cold and hot fracture strength, delamination resistance and adhesion similar to PVO, dimensional stability and, above all, flexibility, with good scale and flexibility. Care must also be taken in determining the latex available.

Experiments carried out on a large number of latexes have shown that vinyl-based copolymers are the most suitable (Example 1 (Fi1221J and Example 2 (Table 1)).
y11222)).

Adequate results are also obtained with styrene-butadiene copolymers and AI[nI]-G copolymers containing all acrylic units.

According to the invention, about 45 to 140 parts (dry weight) of the fiber mixture are used with 100 parts of latex.

The fiber mixture used in the present invention itself has a 60 to 9
It consists of 0 parts cellulose fibers and about 15-5 o i'xs non-cellulose fibers.

The non-cellulose fiber is preferably glass fiber,
Other materials that can be used are, for example, rock wool, polyester fibers and similar other mineral or synthetic fibers.

The support obtained by papermaking from such a basic composition is excellent in the above-mentioned properties, particularly in terms of breakage 11J, strength and peeling resistance.

Good results can be obtained by introducing the flocculant in the following μl order. Zunawara, fiber mixture, 1st
70 times the addition of the flocculant, the latex, the second addition of the flocculant, and the third addition of the flocculant.

For experiments, slightly beaten cellulose fibers, especially 2
50SR and about 6 or 4 mm in length and IU diameter 1
0 to 11 μmσ) glass fiber was used.

However, while the length is 6 to 12 meters, preferably 6 to 6 meters
m and I+j? N 5~15ttm No if 5
X fiber 49. The selection of the type of glass fibers to be used determines the total content of the edge t(Il) in the mixture in a manner known to those skilled in the art.

11 to 70 Tsuku Formation, Tori & J said patent application and corresponding European patent tB M m00006
No. 690) The products listed in the Table 5 can be used (see Table 5). Abrasives, dry strengtheners, silica, wetting agents, preservatives, etc. may also be used in the conventional manner.

The properties of the flocculant used in the present invention and the addition method (
(as well as the number and location of points of introduction), the nature of the latex used, the equipment ζt and the contact time of the product, but the total flocculating agent addition [inlet j-t is usually 1 part latex 1 part 5 = 50 parts.

According to the present invention, it is noted that the preferred composition of the present invention described below (see Table 5, 2) has a dimensional stability against water of less than 0.0% and a curling shrinkage rate of less than 5%. This shows the improvements that should be made (see Table 4).

Those skilled in the art will appreciate the great difficulty that exists in the fact that desired improvements in those properties should not diminish other properties of the product being replaced.

For example, the fact is that as the proportion of glass fibers increases, the mechanical properties quickly weaken, especially with regard to delamination strength, flow resistance and the essential properties of fibers, considering their application as wall coverings. Are known.

In such a case, fluff (flurfjl)P;,
It is also known that when glass fibers are present in very high proportions, a phenomenon known as glass fiber extrusion occurs.

It is therefore surprising that the present invention has achieved incompatible features, or desirable requirements which are known to be inherently contradictory features.

According to the present invention, the above-mentioned "first stage" can be further modified in the second stage [1.
41! I have an interest in carrying out.

These are: surface condition (fuzz formation or glass fiber embossing control), water and plasticizer resistance properties, preservative properties, mechanical strength and stiffness, flexibility (and thus curling characteristics and flexibility).

In order to overcome the curling of products coated with plastisol on the front side, a second stage treatment can preferably be carried out on the back side.

As a second stage treatment, a chemical composition is deposited on the surface or inside by layer separation using a roll, etc. The goal was 17ljl IV・71
Operations such as 1V8 filter, impregnating operation, and overcoating operation may be performed. In particular, the addition of latex or plasticizers is mentioned in the size block.

It is also possible to carry out mechanical treatments such as heat treatment and/or cold or hot finishing or glazing.

A person skilled in the art will understand such technology and know how to select the product to be used according to the desired characteristics.

Usually, the product is 10~1009/m2 in case of single-sided treatment.
(wet state), after drying i.e. 2-60g/m2, preferably 2-2097m and in case of screen treatment 3-4
It is deposited at a ratio of 0.097m.

Hereinafter, the present invention will be explained in more detail based on examples, but these examples are not intended to limit the present invention in any way, and those skilled in the art will be able to The parameters in the present invention are changed to 2.
It is a culm that indicates an instruction that can be transformed into a culm.2)

Examples 1 to 4 A. The compositions used in Examples are shown in Table 1, respectively. The method of implementation corresponding to the experiment shown in Table 1 was as follows.

Fiber mixture: Cellulose resinous I&lli,! l[i (25°SR treated with soda and labeled)
50 parts Glass fiber (4 mn, 11 μm; Vitrofil (■TR0FI:L) OSW) 10 parts Floc forming agent (polyamide/polyamito shrimp chlorpidrine): Nadavin LT
4 parts (approximately 5 minutes at time of contact with latex (see Table 1): [0 parts (approximately 5 minutes of contact time) Floc-forming agent (high molecular weight polyacrylamide) added twice after latex: (] ) The amount to be added to Babala × □ parts (see Table 1)
Therefore, addition of series A of flocculants was carried out. The results are summarized and shown in Table 1.

＼ The chemical properties of the latexes used in Table 1 were as follows.

F11211: Vinyl acetate
54-60w% ethyl/>10
Heichi 16 Vinyl chloride 27
~・63 〃y11222: Vinyl chloride unit 70-90% by weight Methyl acrylate unit 10-60 〃Di]Qudylphthalate (plasticizer) 30=4ON711224: Sutylene unit 60% by weight Butadiene unit
40 #F11225: 'l-#
Acryk-) 87-97, j
'ti, jA% acrylonitrile
1~8wN-methylol acrylate 1~
6 Acrylic acid 1-6 Also, in Table 1, the peeling resistance of Example 6 (F 11224) could not be measured because the plastic sheet separated. In order to overcome this drawback, overcoating had to be carried out while promoting the adhesion of PVO.

In Table 1, the two persimmons that were determined to be desirable to improve with respect to each of the above compositions showed no ν property7, and such a property was determined to be desirable for each of the above compositions. It's more than that
The improvement is particularly warranted for applications where one side has a positive plus decyl coating.

Therefore, that J: Preface 20 of eel weight goods [] C
Dimensional stability in water of materials heated by stove for 2 hours at C
,,accelerated test after 8 minutes immersion in J2) is 0
．． After 20% order (lateral stretch) and footing on one side with plus decile, the product is 2)
The lateral shrinkage exceeded 0% and was enough to cause 71 combs, rolls or curls. A description of such an experiment is given in French Patent Application No. 8212319, Letter I.

Unless otherwise specified in Table 2, it is an aqueous solution.

Examples 5 to 9 Preferred compositions used in the examples are summarized in Table 6.

Therefore, the nature of the flocculant, the amount added, the number of times it was introduced and the place of introduction were varied depending on the nature of the latex used, the equipment and the contact time of the product.

The total amount of the floc-forming agent to be added depends on the properties of the floc-forming agent (particularly the molecular stability of the floc-forming agent, its ionization ability, etc.), but it is preferably 2 to 60 parts per 100 parts of latex. It was ~10.

Vitrofil OSW S is a cellulose fiber made of 25° SR needle M tree bleached with thorium, glass fiber is 4 mm, and glass fiber is 11 μm. Shrimp chlortex to vinyl acetate 54□ 6 [1, i
fil 1%, ethylene 10-16% by weight, vinylc I
J-Lye 1! A copolymer consisting of 27 to 66% polymer, the flocculant added in the second and sixth times is polyacrylamide of crystallite, and the sizing agent is 2 of alkyl ketene of Kl fatty acid. The size of the legs was reduced to 025.

Further, in Example 7, a mixture having the following composition was used in the second stage treatment.

Latex copolymer 1500 parts Vinyl chloride 70-901R Ji
k% methyl acrylate 10-60
(Plasticizer 60-40 #) Fatty acid alkyl ketene duplex 50 parts Flat saw In Examples 8 and 9, a mixture having the following composition was used for the treatment of the second stage 111!7.

Acrylic latex 1500 parts Edylacrylate 87-974j% Acrylonitrile 1-8 N-methylol acrylate 1-6 Acrylic acid 1-6 2 Jm of alkyl ketene of u fatty acid 50 parts Bactericidal product ( Table 4 shows the conventional IJ-containing crow web (Comparative Example 1) and the product according to the present invention (Real H
; Comparison between Examples 5 to 9). The glass web used in Comparative Example 1 was 509/♂ impregnated with 4769/River 2 plastisol. Those skilled in the art will find that products according to the invention are often lighter, less dense and more rigid. The curl test was based on French Patent Application No. 82-12619.

Example 6 (MP 17759) Cellulose yarn 11245 parts Glass fiber (4 mm): 20 parts Latex (same as Table 6): 100 parts Example 7
(MP 17765) (Product with stronger internal bonding force) Cellulose fiber: 31.5 parts Glass fiber (4 mm): 15 parts Latex (same as Table 6): ioo part Example 8 (
MP 17835) (Product with stronger internal bonding force) Cellulose fiber: 31.5 parts Glass fiber (3 mm): 25 parts Latex (same as Table 6): 100 parts Example 6.7
The compositions, methods and results in Tables 5 and 6 are summarized in Tables 5 and 6.The above six compositions according to the invention are also found to be interesting.

In addition, the cellulose used in Table 5, the first flocculant, latex, the second flocculant and the sixth 70° ink forming agent, and the size uniformity H used in Table 6) There was [Tsukasa Fρ-C].

Further, the amount of addition of the flocculant in the sixth round in Table 5 is expressed in dry weight % based on the total dry weight of the composition.

Claims (1)

[Claims] 1 45-14o dry t:'lit part #l [, compound oyohi 100 dry, ? A paper sheet with a high latex content, characterized by containing a tonne of latex. 2) A paper sheet according to claim 1, wherein the fiber mixture comprises 30 to 90 parts by dry weight of cellulose fibers and 15 to 50 parts by dry weight of non-cellulose fibers. 6. A paper sheet according to claims 1 and 2, wherein the non-cellulose fibers are selected from glass fibers, rock wool, polynisder fibers and other mineral fibers or similar synthetic fibers. 4. The paper sheet according to claim 6, wherein the non-cellulose fibers are glass fibers. 5 Glass fiber length of 6-12mm and 5-15μ
Feature #'F Claim 6 or 4 having a diameter of m
Paper sheet described in section. 6 Glass woven front has a length of 6 to 6 mm and a thickness of 10 to 11μ
The paper sheet according to item 6 or 4, having a diameter of +1'F fsf. A composition containing 71 types or 2 or more types of 70 Jl'J ingredients and additives conventionally used in papermaking, in which a part of the floc-forming agent is added after the addition of latex, is processed on a paper machine. The first scope of patent 8i'1 obtained by passing
Term, 2nd J:r(, 6th term, 4th term, 5th term, and 6th term
Paper sheet described in section. 8 The flocculant is aluminum sulfate, polyaluminum chloride, sodium aluminium, calcium aluminate, 5-60% (heavy Jit/volume jfL) solution of a mixture of polyacrylic acid and polyacrylamide, 2-50% of polyethyleneimine. % (weight/volume) solution, copolymer of acrylamide and β-methacrylogyethyl trimedyl 7'mmonium methyl za-A-phate, 2-50% solution of polyamine-dihydrochlorohydrin and diamine-propylmethylamine resin, shrimp 2-50% solutions of polyamide-epichlorohydrin resins made from chlorhydrin, cabrolactano-adipate, diethylenetriamine and/or ethyleneimine, polyamide-polyamine-epichlorohydrin resins made from epichlorohydrin, dimethyl ester, adipic acid and diethylenetriamine A 2-50% solution of shrimp, polyamide 1-bichlorohydrin resin made from chlorohydrin, diethylenetriamine, adipic acid and ethyleneimine, polyamide shrimp made from adivicic acid, diethylenetriamine and a mixture of epichlorohydrin and dimethylamine. 2-50% solution of chlorohydrici resin, cationic polyamide-polyamine resin made from triethylene triamine, fused synthetic f4 of aromatic sulfonic acid and formaldehyde, aluminum acetate, aluminum formate and acetic acid ISψ aluminum, sulfuric acid Claims 1, 2 and 6 selected from a mixture of aluminum and aluminum formate
The paper sheet according to Items 1, 4, 5, 6 and 7. 9 Fiber mixture: cellulose fiber 25°5R5Q dry glass fiber (
4mm, Hμm) 10 Dry 11. +: Floc forming agent added once between tit part (polyamine/polyamide-epichlorohydrin): 1 to 10 dry exposure 11 parts styrene-butadiene copolymer, acrylic yarn 1 to 1 (combined,
Vinyl chloride-ethylene-vinyl 1=: I-
4fGit<lambda from vinyl chloride-acrylate yarn copolymers added with coalescing and plasticizers: 'j Fax: 00 Dry/Wa ■ In-groin floc-forming agent (polyacrylamide): No. Amount added to the vat in the second time 111.1] 3 to 1 dry liter, ・Amount added to the surface in the third time 0.4 to [ ], 8
Dry mulberry? Special #'t' obtained by papermaking from a composition consisting of r<shabu 8? ! A paper sheet according to claim 1, 2, 6, 4, 5, 6, 7 or 8. 10. The paper sheet according to claim 9, wherein the flocking agent (polyamine/polyamide-epichlorohydrin) added at the first time is 4 parts by dry and clean weight. 11 Mixture of fibers: cellulose fiber 25°SR45 dry heavy sensitive glass fiber (
4mm) 20 dry heavy contact latex (56-60% vinyl acetate, 10-16% ethylene
i%, vinyl chloride 27-66% by weight copolymer)
: Claim 1 obtained by papermaking from a composition consisting of 100 dry heavy seams,
The paper sheet according to item 2 or 6. 12 Fiber mixture: Cellulose fiber 25° SR3L5 dry weight glass fiber (4 mm) 15 dry weight parts Latex (vinyl acetate 56-60 Jli kik%1, L-tyrene 10-16ij, 4%, vinyl chloride 27-3
,'l 11 < Iyt % c/) copolymer):
1 obtained by papermaking from a composition consisting of 100 dry I/U parts! A paper sheet according to claim 1, 2 or 6. 16 Fiber mixture: cellulose fiber 25°SR51.5 dry weight glass fiber (6 mm) 25 dry i+t, tit part laterexyl acetate 56-60%, ethylene 10-16%, vinyl chloride 27-56w
1y>% copolymer): 100
A paper sheet according to Claims 1 and 2 and Claim 3, which is obtained by papermaking from a composition comprising a dry heavy electric part. 14 Special features that undergo a second stage treatment consisting of coating operations by spray, size press, blade or roller spreader, impregnation operations and overcoating operations.
Range of a search 1st term, 2nd term, 6th term, 4th term, 5th term,
Item 6, Item 7, Item arQ, Item 9, Items 1 and 0, Item 11, 'rO12 and 2. Paper sheet according to item 15. 15. A paper sheet according to claim 14, which is also subjected to finishing, cold necking or knee polishing, and/or mechanical treatment.