DE3607908A1 - CLEANING COMPOSITION FOR A PRINTING MATRICE - Google Patents

Description

description

The invention relates to a new treatment agent for printing documents, it relates in particular to a cleaning composition, which is useful for the treatment of a printing stencil and a printing underlay material.

A screen to which a photosensitive resin film is applied to form a printing substrate _{/ is / /} is contaminated with sebum from human bodies, oils and dust. When the photosensitive resin film is applied to the stained screen, uneven printing results and a clear print cannot be obtained. Heretofore, the soil has been removed with a neutral detergent as described in Japanese Patent Publication 38506/1977.

However, although the dirt can be removed with the neutral detergent, the screen is with water poorly wettable, and therefore the photosensitive resin film cannot be accurately placed.

Although the screen with an organic acid-containing detergent to achieve excellent Washability and wettability can be cleaned with water, the detergent must be used carefully, because the organic acid is a strong acid.

Under the circumstances, it is an object of the present invention to provide an agent for the treatment of pressure gene available that has a high cleaning power to remove oils, fats and dust from the Screen and an excellent anti-redeposition effect and excellent wettability with Has water and does not make the hands rough.

It has now been found that the cleaning power and the water retention of a treatment agent for printing documents can be significantly improved by incorporating a cationic polymer and an anionic surfactant to form a complex and to increase its adsorbability on a screen.

The cleaning composition object of the invention or preparation is useful for treating a printing matrix and a printing material, in particular a screen, and it is characterized in that it contains 0.1 to 15% by weight of a cationic Polymers, 0.1 to 15 wt .-% of an anionic ten-

sids and the remainder contains water.
15th

The composition or preparation preferably contains additionally 0.5 to 10% by weight of a non-ionic surfactant.

Alternatively, it preferably additionally contains 0.1 to 10% by weight of a non-ionic surfactant and 0.001 to 5% by weight a polymer of maleic acid or maleic anhydride, a copolymer thereof, or a water-soluble one Salt of the polymer or copolymer.

According to one embodiment, the present invention relates to a composition or preparation (hereinafter always referred to as "composition"), which is a cationic polymer, an anionic surfactant, a nonionic Surfactant and a homopolymer of maleic acid or maleic anhydride, a copolymer thereof with a monomers copolymerizable therewith or a water-soluble one Contains salt of the polymer.

When using the treating agent of the present invention dirt can be thoroughly removed from the screen and its wettability with water can be improved

will. Therefore, a light-sensitive screen can be applied to the screen Film can be placed exactly and, as a result, uniformly printed products can be obtained. Sin Another advantage is that the treatment agent can be used safely because it is neutral.

In the case of the cationic polymer used according to the invention it can be any of those having the following functional groups: 10

number 1

No. 2 20

No. 3-

H f ¹

No. 4

No.

No. 10

- pt-j

Among them, the quaternary salts (No. 4) are particularly preferred.

to preferred examples of those used according to the invention Cationic polymers include cationic starches and cationic celluloses of the following general formula

where mean:

A _{1 is} a starch or cellulose residue, R is an alkylene or hydroxyalkylene group R ₁ , R_ and R_, which can be the same or different, each an alkyl, aryl or aralkyl group

group, or which together can form a heterocyclic ring which contains the stick ⁴ -stoffatom in the above form,

X is an anion such as a chlorine, bromine, iodine or sulfate, sulfonate, methyl sulfate, phosphate or nitrate ion and

1 is a positive integer.
5

The cationic starch can be obtained, for example, by reacting starch with glycidyltrimethylammonium chloride or S-chloro-hydroxypropyltrimethylammonium chloride under alkaline conditions. Another method of making the cationic starch involves quaternizing dimethylaminoethylated starch. A
Another method involves the conversion of starch with
4-chlorobutenyl-trimethylammonium chloride.

The cationic cellulose can be obtained, for example

by adding hydroxyethyl cellulose of the above Reaction subjects.

The degree of substitution of the cationic starch or the
cationic cellulose by the cation is 0.01 to 1. In particular, those containing 0.01 to 1, preferably 0.02 to 0.5 cation groups per anhydrous glucose unit are used.

The cationic polymer is in the treating agent
an amount from 0.1 to 15% by weight, preferably from 1
up to 10% by weight.

The cationic polymers used according to the invention also include cationic vinyl polymers of the following formulas:

R *
I.
- £ CH ₂ -

Λ- v

O ^ ^ Yf CH ₃ -3-5Γ t (- 2nd X

Where mean:

R. a hydrogen atom or a methyl group,

Rj-, R _fi and R_, which can be the same or different, each represent a hydrogen atom or a substituted or unsubstituted alkyl group

with 1 to 4 carbon atoms, Y is an oxygen atom or an NH group in

an amide bond,

X the same residues as in the above

Formula (I) have been given, and

m is an integer from 1 to 10;

for CH ₂ - CH - * ».

Th * -ί ^ E, -

in which Rq, R 1 and R ₁₀ /, which can be identical or different, each represent a hydrogen atom or a substituted or unsubstituted alkyl group having 1 or 2 carbon atoms and X has the meanings given in the above formula (I);

(IV)

Γ -

^ H ₃ X

wherein X is as defined in formula (I) above;

1 _(v)

CH ₃

(-CH ₃ Cl
Poly (N-vinyl-2,3-dimethylimidazolinium chloride)

These cationic vinyl polymers can either be used alone or in the form of a mixture of 2 or more thereof can be used in the present invention.

The anionic surfactants which can be used according to the invention include the following:

(1) Straight or branched chain alkylbenzenesulfonates having an alkyl group with 10 to 16 carbon atoms in the Average,

(2) Alkyl or alkenyl ether sulfates with a straight chain or branched alkyl or alkenyl group having 10 to 20 carbon atoms on average to the an average of 0.5 to 8 moles of ethylene oxide, propylene oxide or butylene oxide, or both ethylene oxide also propylene oxide in a ratio of 0.1 / 9.9 to 9.9 / 0.1 or both ethylene oxide and butylene oxide in a ratio of 0.1 / 9.9 to 9.9 / 0.1 aadated have been,

(3) Salts of alkyl or alkenyl sulfates with an alkyl or alkenyl group with 10 to 20 carbon atoms on average,

(4) Olefin sulfonates having an average of 10 to 20 carbon atoms in the molecule,

(5) Alkanesulfonates with an average of 10 to 20 carbon atoms in the molecule,

(6) saturated or unsaturated fatty acid salts with an average 10 to 24 carbon atoms in the molecule,

(7) Salts of alkyl or alkenyl ether carboxylates with an alkyl or alkenyl group with an average of 10 up to 20 carbon atoms to which an average of 0.5 up to 8 moles of ethylene oxide, propylene oxide or butylene oxide or both ethylene oxide and propylene oxide in one Ratio from 0.1 / 9.9 to 9.9 / 0.1 or both ethylene oxide and butylene oxide in a ratio

from 0.1 / 9.9 to 9.9 / 0.1 have been added, (8) t * sulfo fatty acid salts or esters of the following Formula:

H-CHCO ₂ Y! SO ₃ Z

where mean:
y is an alkyl group having 1 to 3 carbon atoms

or a counterion,
Z is a counterion and
R is an alkyl or alkenyl group with 10 to 20 carbon atoms,

(9) Alkyl or alkenyl succinic acid salts with an average of 10 to 22 carbon atoms.

The counter ions of the above-mentioned anionic surfactants include alkali metal ions such as sodium and potassium ions; Alkaline earth metal ions such as calcium and magnesium ions; the ammonium ion; and alkanolamines with 1 to 3 alkanol groups, each having 2 or 3 carbon atoms contain;

(10) The following phosphoric acid ester surfactants:

No. 1: Acid alkyl (or alkenyl) phosphates:

0
(R ¹ O) _n -P- (OH) »·

where R 'is an alkyl or alkenyl group with 8 to 24 carbon atoms, n' + m 'is the number 3 and n ^{1 is} a number from 1 to 2,

No. 2: alkyl (or alkenyl) phosphates:

! I

CH ¹ O) - P- (OH) "-

where R ¹ is defined as above, η ^ + ηι " ^{1 is} the number 3 and n ¹ 'is a number from 1 to 3, and 10

No. 3: Salts of alkyl (or alkenyl) phosphates:

0
CH'0) .- P-COM) - ¹

wherein R ¹ , n ¹ 'and m ¹ ' are as defined above and M is Na, K or Ca.

Among the above compounds, those having a high complexing ability are preferred. Particularly The sodium salts of the abovementioned alkylbenzenesulfonic acids (1) are preferred.

The anionic surfactants are used in an amount of preferably 0.1 to 15 wt % By weight, used.

Regarding the nonionic surfactants used according to the invention include the following:

1) Polyoxyethylene alkyl or alkenyl ethers with an alkyl or Alkeny! group with an average of 10 to 20 carbon atoms, about 1 to 20 moles of ethylene oxide are added,

2) polyoxyethylene alkylphenyl ethers with an alkyl group with an average of 6 to 12 carbon atoms to which 1 to 20 mol of ethylene oxide have been added,

3) polyoxypropylene alkyl or alkenyl ethers with a -_ Alkyl or alkeny groups with an average of 10

up to 20 carbon atoms to which 1 to 20 moles of propylene oxide have been added,

4) Polyoxybutylene alkyl or alkenyl ethers with an alkyl or alkenyl group with an average of 10 to

20 carbon atoms, to which 1 to 20 moles of butylene oxide are added,

5) non-ionic surfactants with an alkyl or alkenyl group with an average of 10 to 20 carbon atoms, to a total of 1 to 30 moles of ethylene oxide and

Propylene oxide or butylene oxide (the ratio of

Ethylene oxide to propylene oxide or butylene oxide is 0.1 / 9.9 to 9.9 / 0.1) are added,

6) higher fatty acid alkanolamides of the general formula given below and alkylene oxide adducts thereof:

where R ^ _{1 is} an alkyl or alkenyl group having 10 to 20 carbon atoms, R ' _{2 is} H or CH ₃ , n., an integer from 1 to 3 and iru an integer from 0 to 3

mean,
7) sucrose fatty acid ester, which is a fatty acid with

an average of 10 to 20 carbon atoms and Sac

charose contain,

8) Glycerol monoester of fatty acids, which is a fatty acid with an average of 10 to 20 carbon atoms and Contain glycerin, and

9) Polyoxyethylene-polyoxypropylene block copolymer surfactants of the following general formulas:

HO (C ₂ H ₊ Q) _a - (C ₃ HiO) b _{- (C 2} H ₊ O) _C H

JN-CH ₂ CH ₂ -N ^

Hy (O ₊ H ₂ C) -

wherein a, b and c are each an integer from 2 to
20 and χ and y are each an integer from 2 to 20
mean.

Among the above non-ionic surfactants are
those with a high affinity for the complex are preferred. Particularly preferred are polyoxyethylene alkyl or
-alkenyl ether (1).

The nonionic surfactant is used in an amount from 0.5 to 10% by weight, preferably from 1 to 8% by weight, is used.

Among the homopolymers of maleic acid or maleic anhydride, the copolymers of the same with monomers copolymerizable therewith and the water-soluble salts of these polymers, which are used in the present invention, are am
most preferably the homopolymers, copolymers and their salts having a molecular weight of from about 1,000 to about
100,000, which is represented by the general formula:

where mean:

R ₁ , R ₂ , R ₃ and R. each represent a hydrogen atom or a

substituted or unsubstituted alkyl group (R ₁ and R ₃ can together

form a cycloalkyl ring), carboxyl group or alkoxyl group of 1 to carbon atoms, M. a hydrogen atom, an alkali metal

or an alkanolamino group and

η and m each 0 or a positive number where

at n / m is 1/10 to 1/30.

The above general formula represents not only block polymers but copolymers including of random copolymers (and homopolymers if m = 0)

Examples of the above copolymers include the following:

~ T C H C n j r Cn CH ■ * τ

Vi ι- / Λ / \ / »

COONa COOMa CH ₂ CH ₂ -

. CS =

n / m = l / l, HG about 6,000

1 VjII Ln i-r -— La Lrii -7

V! ι / Λ / \

COONa COOHa CH ₂ CH ₂

CH ₂ -CH ₂

n / m = l / l, MG about 4,000

4— CH - Cn Η— CH- CH _S 4-

Vl I / η \ I / m.

COONa COONa CH-CH ₃

CH

n / m = l / l, MG about 5 QOO 10

~ \ CH - CH j - r - CH - CH: ~ 7

\ ι ι / A ι ■ h

COONa COONa OCH ₃ n / m = l / l, MG about 10,000

~ 7- CH C d ι r Cd CΗ ζ

VlI / n \ -I

COONa COONa COOM-a

n / m = 1/20, "MG about 15 qqq

Particularly preferred among them are copolymers of cyclopentene and cyclohexene. They are used in an amount of 0.001 to 5% by weight, preferably from 0.05 to 1% by weight, used.

The treatment agent according to the invention can also thickeners, Pigments, colorants, flavorings, germicides, antiseptics and the like. If so desired is.

The remainder consists of water or a mixture of water and a water-soluble solvent.

Examples of suitable water-soluble solvents include lower alcohols / such as methanol, ethanol, propanol, Isopropanol and butanol; Carbitols, such as butyl mono-, di-or -triglycols; Cellosolves such as methyl cellosolve and ethyl cellosolve; and acetone.

Examples

The invention is explained in more detail below with reference to the following examples, but without them to be limited.

The numbers given in the tables below mean% by weight with the exception of the cleaning rates. 15th

Examples 1 to 3 and Comparative Examples 1 and 2

The cleaning power and the wettability with water of the compositions or preparations according to the invention in the following Table I were examined, the results given in Table I being obtained .

Procedure for determining the cleaning power

A rapeseed oil was uniformly applied to the surface of a Polyester screen applied. The screen was impregnated with one with 5 g of a detergent Sponge rubbed (5 back and forth passes), washed with water and dried. The cleaning power is shown as the cleaning rate, which is the difference in weight before and after cleaning according to the the following formula was calculated:

D (cleaning rate in%) -

_ Weight of rapeseed oil after cleaning (g) Weight of rapeseed oil before cleaning (g)

Method for determining wettability with water

A polyester mesh screen, cleaned as above, was immersed in water and slowly pulled out to remove it Determine wettability with water using the following criteria.

O: complete wetting

^: the water was partially repelled and

X: the water was completely repelled

Table I.

composition

See Ex.

Examples

Cationic starch

Sodium alkyl (C _{1 2} ) benzenesulfonate

Sodium alkyl (C ₁₉ ) sulfate '-

tap water (S) 95 95 90 98 94 Cleaning rate with water 31 65 83 80 73 Wettability X X 0 0

-V-GHa

*) (remaining group of starch ^ -OCH-CH-K-CH ₃ Cl

I ^X CH ₃ OH

Examples 4 and 5 and Comparative Example 3

The cleaning power and the wettability with water of the compositions given in Table II were

the investigated, the results shown in Table II were obtained.

Table II

^ Examples of composition ex.

Cationic starch
10

'Sodium-alky! (C ₁₂ ) benzene sulfonate

Polyols thy lenalkyl-. ether

tap water 90 90 87 .Cleaning rate (%) 72 83 95 Wettability with water X ' O O

*) vlg. Table I.
**) C ₁₂ , EO = 3.

Examples 6 and 7 and Comparative Examples 4 and 5

__ The cleaning power and the wettability with water each of the compositions given in the following Table III were examined and the in the results given in Table III were obtained.

Method for determining the anti-redeposition effect

400 cm ^{3 of} tap water and 0.1 g of carbon black were introduced into a 500 cm ³ beaker and stirred with a magnetic stirrer. The cleaned polyester screen was immersed therein and then slowly pulled out, and its anti-redeposition effect was determined using the following criteria:

* O '- No soil redeposition was observed,'& _: Partial soil redeposition j was observed

and

5 ^x . ^: . redeposition of dirt was observed over the entire surface.

Tabel composition III .E.g. 5 ■ ι 2hen- '■ Η
P ' Q) Examples 7th 10 cationic starch * ' ■ i -cn 6th '5 Natriuirralkyr (C ₁ ") benzenesulfonate ·. See . i angry;
organ: 5 5 Polyoxyalkylene alkyl ether * * 4th component
commercial cleanser (
tend a
Acid) 5 3 Cyclohexene / anhydrous Na maleate
(1: 1) (MG = 4000) ■ h
cn ι, α 72 3 0.1 15th Vinyl acetate / anhydrous Na maleate
(1: 2) (MG = SOOO)
tap water rH (3 (O
ti $ cn Δ ; 86.9 Cleaning councils (%) 8 ° 'S X 0.5
36 .; 97 Wettability with water i it
holder
Tens ic 96 O 20th An t i redeposition ef f ect commercial
Agent (ent
ionic O O 63 O X X

• ^ (remaining group of starch) OCHsCa-N-CH ₃ CI

I- ^X CE ₃

30 ^0S

** C, _of EO = 8

Examples 8 and 9 and Comparative Examples 6 and 7

Each of the compositions given in Table IV below in terms of their cleaning ability, wettability with water and anti-redeposition effect investigated and the results obtained are given in Table IV.

Table IV

Composition

Vg Example -

Examples

8 ■

Cationic starch

■ 5

Sodium alkyl (C ₂ ) benzenesulfonate polyoxyethylene alkyl ethers

Polyoxyethylene nonylphenol (C _Q ; EO = 12) " ^y

Cyclopentene / anhydrous Na maleate (1: 1) (MS = 6000)

Tap water purification rate (%)

Wettability with water anti-redeposition effect

5 - 5

5. 5

1 0. .1 0 .5 85 94 • 84 .9 86 .5 73 70 94 97 X X O O X X O G

*) see table III **} see table III

Although the invention has been explained in more detail above with reference to specific preferred embodiments, however, it is self-evident to the person skilled in the art that it is by no means restricted to this, but that this can be changed and modified in many respects without thereby departing from the scope of the present invention is left.

Claims (4)

Kao Corporation 14-10, Nihonbashi-Kayabacho 1-chome, Chuo-ku, Tokyo, Japan Cleaning composition for a printing matrix. Claims 1. Cleaning composition for a printing matrix, characterized in that it is 0.1 to 15 % By weight of a cationic polymer, 0.1 to 15% by weight of one anionic surfactant and the remainder water. 2. Cleaning composition according to claim 1, characterized in that it additionally contains 0.5 to 10% by weight of a Contains non-ionic surfactant. 30th 3. Cleaning composition according to claim 1, characterized in that it additionally contains 0.1 to 10% by weight of a nonionic surfactant and 0.001 to 5% by weight of a polymer of maleic acid or maleic anhydride, a copolymer thereof or a water-soluble salt of the polymer or copolymer. 4. Cleaning composition according to one of claims 1 to 3, characterized in that the cationic polymer Asamstrasse 8, D-8000 Munich 90 Toiof / -ir> mpcn / nRQ \ Patent attorney Dr. Inq. Dipl.-Ing. A. SoIf (Munich) is selected from a group consisting of a cationic starch, a cationic cellulose and a cationic vinyl polymers.