JPS58132198A - Neutral size agent - 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 a neutral sizing agent. More specifically, cationic self-fixing that does not require a fixing aid - Neutral sizing agent.

Most of the sizes currently available on the market require sulfuric acid as a fixing aid. When sulfuric acid is used as a fixing aid, the strength and durability of the paper and the setting properties of ink during printing deteriorate. Father, IJ of irrigation water? As the cycle progresses, in systems using sulfuric acid, the quality of the water inevitably deteriorates, and the effectiveness of the sizing agent also deteriorates. Therefore, papermaking in the neutral range, which does not require sulfuric acid bands, is
I can pass.

As a neutral sizing agent, a self-fixing cationic sizing agent and a reactive m? Anti-inflammatory agents are commercially available.

Although it has a size effect, it causes a decrease in paper strength, is high 1, and is complicated to work with.

On the other hand, in recent years, paper has become increasingly lightweight, and at the same time its opacity and
As printability came to be demanded, alkaline papermaking using carbonate lysium as a filler came to be used. In the case where calcium carbonate is used as a filler, sulfate cannot be used as a fixing aid, and even if a sizing agent is used, its effect cannot be fully demonstrated.
Ta.

For this reason, an internal sizing agent that uses neutral paper or calcium carbonate as a filler and is fully effective even in nine-alkaline paper making is lI!
desired.

Therefore, the present inventors conducted extensive research into a neutral sizing agent that is inexpensive, does not reduce paper strength, and can provide a sufficient sizing effect even in neutral or alkaline paper making. The desired product can be obtained by simply blending an emulsion carbon obtained by craft copolymerizing a monomer represented by the following general formula with a cationic S-based polymer compound. I completed the original @ with the heading.

That is, the present invention provides an emulsion l obtained by copolymerizing monomers represented by the following general formulas and (j3) into a water-soluble molecular polyhydrosilicide.
This is a neutral sizing agent consisting of a cationic water-soluble polymer compound and a cationic water-soluble polymer compound.

(In the formula, R1 is II, 0118. or 'mHs: R
* is E or 0111: "s is g or O! 11:n is an integer from 4 to 8.) Examples of the water-soluble polymeric polyhydroxy compound used in the present invention include potato starch, milkweed starch, tapioca starch, etc. natural starches, their decomposition proboscis, etherified starch, esterified starch, oxidized starch, chemically modified powders such as dialdehyde, cellulose conductors such as methylcellulose, carboxymethylcellulose, hydrodiethylcellulose, etc. , Dechustofun,
Examples include polyvinyl alcohol in mold-producing polystyrene such as Plu2-no.

The body component used in this book is styrene.
Although moths are also advantageous, vinyl toluene/α-meterstyrene and the like are also used. As component (j3), either acrylic or methacrylic acid alkyl esters can be used. The cationic water-soluble polymer compounds to be blended include polychlorohydrin resin, cationic polyacrylamide, polyethyleneimine, cationic dialdehyde starch, cationic steel powder, dicyandiamide formaldehyde resin, etc. can also be used.

In the graft copolymerization of the present invention, the proportion of the carbonaceous compound in the water-soluble polymer polyhydride is required to be 5 to 50 moles.

When the amount is 50 mole or more among 5 mole or less, the improvement effect of the 4t size becomes opaque. The ratio of the parent and body components is required to be 5 to 85 moles. 5 mol or less, acrylic acid,
Alternatively, homopolymers of alkyl esters of methacrylic acid are likely to be formed, making it difficult to form a stable emulsion, which is undesirable. - Above 1,850 moles, the size effect becomes opaque.

Father, the amount of cationic water-castable molecules to be blended should be 5 to 5 oll's relative to the solid content of the emulsion.
- more preferably 10 to 20 weight - is l1lt
L.

sm in the graft copolymerization reaction of the present invention is water alone,
Alternatively, a mixed solution consisting of water and a lower alcohol having 1 to S carbon atoms can be used.

In addition, as a polymerization initiator, 27th Liwam salt, persulfuric acid, Harukasulfuric acid sulfite, hydrogen peroxide, 2.2'-7 nobisu(2-amidinopropane) dihydrochloride, azobisisobutyro Nitrile and the like can be used and polymerization can be carried out in a conventional manner at a concentration of 50 to 100C.

Although this graft copolymerization reaction can be carried out using a suitable emulsifying steel for monomers, a stable emulsion can be obtained by self-emulsification during the reaction process even without using an emulsifier. Therefore, considering the negative effects of emulsified steel in practical use, it is better not to use an emulsifier when considering economic efficiency.

Next, a manufacturing example of the neutral sizing agent of the present invention and #t.

Let me explain about the inside of the ship. All reported percentages are weight percentages.

Manufacture of emulsion f41 Oxidized starch M13-3600 [manufactured by Nippon Shokuhin@, moisture 12.6] in a 94-eye flask equipped with a stirrer, temperature needle, reflux condenser and nitrogen blowing tube 1 K5 F and water 550
f was added and the temperature was raised by 80CK to dissolve the oxidized starch.

After cooling the oxidized acid *S liquid at 5oC1, styrene 5 & 2
F, and n-butyl acrylate 01F were added and mixed. After removing oxygen in the reaction system using hydrogen, aoc
ammonium persulfate L1 as a polymerization initiator.
11ft - 500fK of water was dissolved and added in 60 minutes. Furthermore, the reaction was carried out at 80C for 6 hours while flowing nitrogen. After cooling, adjust the concentration with water to create a stable emulsion with a solid content of 10-4.
tiger.

Emulsion production example 2 Oxidized #11M13-3600 in the same equipment as production 111.
．． 5L6f and water! 00f was added and the temperature was raised to SaC to make the oxidized starch to III#. After cooling the oxide #II solution to SOC, styrene 27. Of and 2-ethyl were combined by adding 8 LOf of cuclacrylate. After removing 0tSS in the reaction system using nitrogen, the temperature was raised to aO'-1, and 1.57F of potassium persulfate was added as a polymerization initiator to 500tK of water.
IIWN was added in 60 minutes. Furthermore - 5 hours on aOC while climbing the mountain? My friend reacted on OC for 5 hours.

After cooling, the temperature was adjusted with water to obtain a stable emulsion with a solid content of 10°.

Emulsion Production Example 5 In the same apparatus as Production Example 1, dialdehyde # powder (Nippon Carlit-Yuyu, oxidation degree 85-1 moisture 10, hereinafter abbreviated as DA8) was added IIIF and water 880F, and the temperature was raised to 90C. to dissolve DAB. After cooling the DAsil solution at 50 Ct, add medium syl acrylate IQAOf to styrene 3S4f and 2-ethyl and mix. After removing 1111A in the reaction system using nitrogen, the temperature was raised at aoct and the polymerization initiator 2.2'-Azobis-(2-aidinopron(one) dihydrochloride tssr) was dissolved in 500 fKII of water and added over 60 minutes.
Time passed. After cooling, the mixture was concentrated with water to obtain a stable emulsion with a solid content of 10.

Emulsion m1ll creation example 4 J&1! Polyvinyl alcohol t was added to the same equipment as H1.
-0S (Electrochemistry 4-1 Moisture 5s, hereinafter abbreviated as PV) 2.5F and 850 ft of water, heated to 90 (1') to dissolve the PV. After cooling at 5OC1,
Vns7.4f, 2-ethyl acrylate 1G
&6t was added and mixed. In the reaction system using nitrogen! 1
After removing the element, potassium persulfate t was added as a polymerization initiator,
48F was dissolved in 500fK of water and added. a from 50C
The temperature was gradually raised to OC, and the mixture was reacted with SaC for 7 hours while flowing nitrogen. The emulsion tP having a solid content of 10 was obtained by adjusting the concentration with water.

Emulsion production example 5 In the same equipment as production fI11, add 17 pieces of water and 1 powder.
snt and 840f of water were added and dissolved in 90CKJ11. Cool to 30C and add styrene 4L6f.

2-Ethylhexyl acrylate 91 (11?t) was added. After JIIIA was removed from the reaction system using a sieve, potassium persulfate 1.5f was added as a polymerization initiator.
0 t K11 and alft* 5OCLsrsc
The temperature was gradually raised at *, and the reaction was continued for 10 hours while flowing nitrogen. A 1* emulsion with a solid content of 10 was prepared by dipping 11 degrees with water.

Emulsion Production Example 6 Hydroxyethyl cellulose was added to the same equipment as Production Example 1.
Unicel QP-9 (Daicel@m, moisture 6s) s! L7
Add 850f of water and add 90C of water.
i.

Just in case. After cooling to 30C, medium syl acrylate 81f was added to styrene 271.2 Yanityl and heated. After removing Al in the reaction system using nitrogen, the temperature was raised to 80G, and 1 qt of potassium persulfate and 7fYt of water were added as polymerization initiators.
QQfKfdtllt, C60 minutes. Further, the reaction was carried out for 6 hours in aOC while flowing nitrogen. After cooling, adjust the roughness with water to obtain a stable emulsion with a solid content of 159g.

Ma row 7 Production of cationic starch 1IIi Milkweed sorghum Ia flour (moisture 14%) 15 melon 92% in the same equipment as Example 1! 591 salt 1j12547 t
, add water S4 & 2f and tiger. The temperature was raised to 50℃ and the reaction was carried out for 6 hours.After the 0 reaction, the temperature was cooled to 5℃, and 21.8f of the 48% sodium hydroxide solution was added to pI! I changed it to Z3.

Next, the temperature was raised to 850°C and the *a powder treated with hydrochloric acid was bathed for 50 minutes. After cooling to 40c, 5-ri ao-2-hydroxypropylammonium chloride hydrochloride 15a3f,
A 48m sodium hydroxide solution at 8°F was added, the temperature was raised to 50C, and the mixture was reacted for 5 hours.

50CK cold Mf &, ss * jlljI! 1s t
(The pH was lowered to pH by adding water. The total weight was adjusted to 1000PK by adding water.
Obtain 59111 liquid.

Production 918 Synthesis of cationic DAB M4aH1<mo flc DAli 2ot (
aI conversion [8S-1 moisture 125k) and water 180Fl added, t
, tpoctK% warmed to +l [L, 9 m30 After cooling with C1, difur T test #41est@1ooto dissolved in water,
Te a addition * bale s.

Stir for a minute. After the mixture was injected into pnz5, the concentration was adjusted with water to obtain a 1osIllI solution of cationic DAs.

Manufacturing example? Synthesis of cationic polyacrylamide 111
In a similar apparatus to 1911, isopropyl alcohol 5-
Add 6F and 50t of water and mix. After removing the IN element in the reaction system using nitrogen, the temperature was raised to 60°C. Furthermore, pour 9 ** and hold at 60 (: 50 mounds, 57 f1 dimethylaminoethyl methacrylate, 7.1 t acrylamide
was dissolved in 20 fKg of water and added over 1 hour. ,father,
At the same time, add ammonium persulfate α18t to water at 5 or K.
The mixture was dissolved and added over 1 hour. After reacting at 60C for 5 hours, the mixture was cooled to 25C and concentrated with water to obtain a 15% cationic polyacrylamide solution.

Comparative Example 1 73 (5,15f, styrene 5
2. Add and mix Of% n-butyl acrylate 5 & 4t. After removing the acid lA in the reaction system using **8
The temperature was raised to 0C, and 2,2'-azobis-(2-amidinopropane) dihydrochloride α9t was added to water as a polymerization initiator.
tKfllllll shite b o minte s addition, ri.

Furthermore, I reacted with SaC for 6 hours while doing ffl*ll.

After cooling, the mixture was boiled once with water to give a milky white emulsion.

Ratio 411! Example 2: 400 tons of water and 5 L of styrene in the same equipment as in Production 1.
2t, medium acrylate to 2-ethyl! 2t.

Emar O [manufactured by Kao Atlas@] cL6t as an emulsifier
, Emulgen-147 (manufactured by Kao Atlas ■) (L6F) was added and mixed. After removing oxygen in the reaction system using nitrogen, the temperature was raised at aoC1, and 2.21-azobis-(2- amidinopropane) dibase Ill salt a!f
Dissolve 500ml of water and add over 60 minutes. Furthermore, 5 hours at aoC while flowing nitrogen? The reaction was carried out in OC for 5 hours.

After cooling, water was added and the mixture was concentrated to give a milky white colored emulsion.

Application row 1 Production rows 7 to 9 and the commercially available cationic water-soluble molecular compound were converted to solid content based on 80 parts of the solid content of the emulsions obtained in production f111 to 6 and comparative example 1.2. So 2
The effects of the present invention's neutralizing agent B, which is a blend of 0 parts, a commercially available emulsion-type neutralizing agent, and B on neutral paper making were investigated.

The test conditions are as follows.

Pulp: NBKP/LBKF=+50150, 3
Water for 0°dR: pH &? ~10 tsubo IIi: 60 Height size agent: Pulp 191 addition paper machine: Tatsupi standard machine drying:
Dry for 5 minutes with a rotary drum dryer
KK test: Compliant with TXB F-8122/Ill
Tensile strength test: Based on JIf3 F-81134C Dry tensile strength test: Based on JIf3 F-81134C Measurement results are shown in Tables 1 to 5.

Table 1 Neutral paper making Table 2 Neutral paper making a) Polyamide/polyamine/epichlorohydrin wood made by Kymen 557HC Dick Percules b) Cationic polyacrylamide produced by the method of Production Example 90) Epo(N D-5000) (Polyethylene inn manufactured by Nippon Shokubai Kagaku 1 Gyo) d) Cationic dialdehyde #powder produced by the method of Production Example 8) Cationic starch produced by the method of Production 9'17 f) Neofix FP ( Dicyandiamide-formaldehyde resin manufactured by NICCA CHEMICAL CO., LTD.] Application example 2 Kaimen 5 was added as a cationic waterborne polymer compound to 80 parts of the solid content of the superior emulsion in Production Examples 1 to 6.
The effectiveness of a non-explosion @ sizing agent made by blending 20 parts of 57H in terms of solid content with a commercially available neutral sizing agent B(1) in alkaline paper making was compared.

The two subjects of the test are as follows.

Valve: NBKP/LBKP==50150jO'
SR term Category: Calcium carbonate vs. pulp 20 ml water: pH 7,6-&0 Sizing agent: vs. pulp 1 sludge addition paper fIA: Tatsupi standard machine drying
: Rotary drum dryer 100CxSsa Size test: J Engineering 8 According to F-8122 Wet tensile strength test: According to TIS P-8135 Dry tensile strength test: From J According to F-8113 Measurement results are shown in Table 4 I have summarized.

Table 4 Alkaline paper making

Claims (1)

[Claims] (1) An emulsion obtained by graft copolymerizing monomers of the following general formulas) and (B) to a water-soluble polymer polyhydroxy compound and a cationic water-soluble polymer A neutral sizing agent consisting of a molecular compound. (In the formula, R1 is 11.OH, or 0.II, : R,
is H or OH, : R1 is H or OH, : II is 4 to 8
indicates an integer. ) (2) The water-soluble polymeric polyhydroxy compound is natural soap powder or chemically modified starch powder.
11JJ-neutral sizing agent. ' (3) 4W where the water-soluble polymeric polyhydroxy compound is a cellulose derivative! The neutral sizing agent according to item 1. (4) The neutral sizing agent according to claim 1, wherein the water-soluble polymeric polyhydroxy compound is polyvinyl alcohol. (5) The neutral sizing agent according to claim 1, wherein the cationic water-soluble polymer compound is a polyamide boriaine epichlorohydrin resin. (6) The neutral sizing agent according to item 1, wherein the cationic water-soluble polymer compound is a cationic polyacrylide. 7゜(7) A neutral sizing agent for the first Sakiki chess game, wherein the cationic water-soluble polymer compound is polyethyleneimine. (8) A neutral sizing agent of Patent Application No. 11J11, wherein the cationic water-soluble polymer compound is a cationic dialdehyde. (9) When the cationic water-soluble polymer compound is a cation powder, the range of WIf restrictions The neutral sizing agent according to item 1. (Claim 31g in which the cationic water-soluble polymer compound 1 is a dicyandiabado-formaldehyde resin)
The neutral sizing agent according to item 1.