CA1252602A - Sizing agent suitable for use in paper making - Google Patents
Sizing agent suitable for use in paper makingInfo
- Publication number
- CA1252602A CA1252602A CA000503137A CA503137A CA1252602A CA 1252602 A CA1252602 A CA 1252602A CA 000503137 A CA000503137 A CA 000503137A CA 503137 A CA503137 A CA 503137A CA 1252602 A CA1252602 A CA 1252602A
- Authority
- CA
- Canada
- Prior art keywords
- group
- sizing agent
- surface active
- alkyl
- ionic surface
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 238000004513 sizing Methods 0.000 title claims abstract description 50
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 36
- 239000004094 surface-active agent Substances 0.000 claims abstract description 24
- 229940014800 succinic anhydride Drugs 0.000 claims abstract description 20
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical class ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims abstract description 18
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 11
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract description 10
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 21
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 19
- -1 polyoxyethylene Polymers 0.000 claims description 17
- 239000003995 emulsifying agent Substances 0.000 claims description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 11
- 125000005037 alkyl phenyl group Chemical group 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- GELKGHVAFRCJNA-UHFFFAOYSA-N 2,2-Dimethyloxirane Chemical compound CC1(C)CO1 GELKGHVAFRCJNA-UHFFFAOYSA-N 0.000 claims description 5
- 229920006319 cationized starch Chemical group 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 238000007259 addition reaction Methods 0.000 claims description 3
- 125000000129 anionic group Chemical group 0.000 claims description 2
- MRXPNWXSFCODDY-UHFFFAOYSA-N 2-methyl-2-phenyloxirane Chemical compound C=1C=CC=CC=1C1(C)CO1 MRXPNWXSFCODDY-UHFFFAOYSA-N 0.000 claims 2
- 239000000203 mixture Substances 0.000 abstract description 21
- 230000000694 effects Effects 0.000 abstract description 8
- 230000007774 longterm Effects 0.000 abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052799 carbon Inorganic materials 0.000 abstract description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 16
- 239000000839 emulsion Substances 0.000 description 11
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 9
- 150000002148 esters Chemical class 0.000 description 7
- 229920001451 polypropylene glycol Polymers 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000001804 emulsifying effect Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000005215 alkyl ethers Chemical class 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 150000001733 carboxylic acid esters Chemical class 0.000 description 3
- 239000004359 castor oil Substances 0.000 description 3
- 235000019438 castor oil Nutrition 0.000 description 3
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 3
- 229920000768 polyamine Polymers 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 239000013055 pulp slurry Substances 0.000 description 3
- RINCXYDBBGOEEQ-UHFFFAOYSA-N succinic anhydride Chemical class O=C1CCC(=O)O1 RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 description 3
- 150000005846 sugar alcohols Polymers 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 229920006317 cationic polymer Polymers 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- LTUMRKDLVGQMJU-VHSABMJYSA-N (5z,9z)-6,10,14-trimethylpentadeca-5,9,13-trien-2-one Chemical compound CC(C)=CCC\C(C)=C/CC\C(C)=C/CCC(C)=O LTUMRKDLVGQMJU-VHSABMJYSA-N 0.000 description 1
- GPFVWKXABQQNEM-BMRADRMJSA-N 3-[(e)-16-methylheptadec-1-enyl]oxolane-2,5-dione Chemical compound CC(C)CCCCCCCCCCCCC\C=C\C1CC(=O)OC1=O GPFVWKXABQQNEM-BMRADRMJSA-N 0.000 description 1
- YAXXOCZAXKLLCV-UHFFFAOYSA-N 3-dodecyloxolane-2,5-dione Chemical compound CCCCCCCCCCCCC1CC(=O)OC1=O YAXXOCZAXKLLCV-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical group C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920002717 polyvinylpyridine Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003839 salts Chemical group 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000003509 tertiary alcohols Chemical group 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Paper (AREA)
Abstract
Abstract of the Disclosure A composition useful as a paper sizing agent comprising a substituted succinic anhydride of the formula:
Description
3~'~5'~ f~
BACKGROUND OF THE INVENTION
The present invention relates to a sizing agent suitable for use in paper ma~ing, and more particularly to a paper sizing agent comprising a substituted succinic anhydride and an emulsifier, which is capable of exhibiting an excellent sizing effect even after stored for a long term.
Various materials have been used for sizing paper. In recent years, sizing using a dicarboxylic acid anhydride has been proposed.
Dicarboxylic acid anhydrides such as substituted succinic anhydrides, which have been used for sizing paper in neutral pH region, have been used usually in the form of an aqueous emulsion by emulsifying in water using an emulsifier such as a surface active agent or cationized starch and a homogenizer or homomixer. It is known that if the dicarboxylic acid anhydride is previously admixed with an emulsifier and stored in the form of a mixture, the emulsifying ability is lowered in a short term and, therefore, the sizing effect is also lowered.
It is an object of the present invention to provide a paper sizing agent comprising a substituted succinic anhydride and an emulsifierl which can exhibit an excellent sizing effect even after stored for a long term.
The above and other objects of the present invention will become apparent from the description hereinafter.
SUMMARY OF THE INVENTION
It has now been found that when a non-ionic surface active agent having a terminal tertiary hydroxyl group is used as at least one component of the emulsifier for emulsifying a substituted succinic anhydride, an excellent sizing effect is obtained even if they are stored in the form of a mixture for a long term.
The term "terminal tertiary hydroxyl group" as 5~ 2 _ 3 used herein means a terminal hydroxyl group bonding to tertiary carbon, in other words, a tertiary alcohol residue represented by the formula: -I-OH positioned at the molecular end.
In accordance with the present invention, there is provided a sizing agent comprising a substituted succinic anhydride of the formula: (I):
R-C~- C~
10 O=C C=O (I) \0/
wherein R is a hydrocarbon group having at least 6 carbon atoms selected from the group consisting of an alkyl group, an alkenyl group, an aralkyl group or an aralkenyl group, and an emulsifier comprising a non-ionic surface active agent having a terminal tertiary hydroxyl group.
DETAILED DESCRIPTION
In the above substituted succinic anhydrides of the formula (I)~ those having the substituent R which is a C6 to C30 alkyl or alkenyl group, especially a Cl2 to C24 alkyl or alkenyl group are preferred.
Representative examples of the substituted succinic anhydride (I) are, for instance, dodecyl succinic anhydride, n-hexadecyl succinic anhydride, n-octadecenyI
succinic anhydride, isooctadecenyl succinic anhydride, l-methyl-2-pentadecenyl succinic anhydride and l-propyl-2-pentadecenyl succinic anhydride. The substituted succinicanhydrides may be used alone or in admixture thereof.
In the present invention, a non-ionic surface active agent having terminal tertiary hydroxyl group is employed as at least one component of the emulsifier used for emulsifying the compound (I).
The non-ionic surface active agent having terminal tertiary hydroxyl group can be prepared, for instance, by addition reaction of usual non-ionic surface .
S~
active agent and isobutylene oxide or ~-methylstyrene oxide, but the process for the preparation thereof is not limited thereto.
Representative examples of the non-ionic surface active agent used as a raw material in the above reaction are, for instance: ~
polyoxyethylene alkyl ether which is an adduct of 3 to 40 moles of ethylene oxide with an alcohol having a C6 to C20 alkyl group;
polyoxypropylene alkyl ether which is an adduct of 3 to 40 moles of propylene oxide with an alcohol having a C6 to C20 alkyl group;
polyoxypropylene~polyoxyethylene alkyl ether which is an adduct of 3 to 40 moles of a mixture of propylene oxide and ethylene oxide with an alcohol having a C6 to C20 alkyl group;
polyoxyethylene alkylphenyl or aralkylphenyl ether which is an adduct of 3 to 40 moles of ethylene oxide with an alkylphenol or aralkylphenol having a C4 to C28 alkyl or aralkyl group;
polyoxypropylene alkylphenyl or aralkylphenyl ether which is an adduct of 3 to 40 moles of propylene oxide with an alkylphenol or aralkylphenol having a C4 to C28 alkyl or aralkyl group;
polyoxyethylene-polyoxypropylene alkylphenyl or aralkylphenyl ether which is an adduct or 3 to 40 moles of a mixture of ethylene oxide and propylene oxide with an alkylphenol or aralkylphenol having a C4 to C28 alkyl or aralkyl group;
polyethylene glycol carboxylic acid ester which is an adduct of 3 to 40 moles of ethylene oxide with a carboxylic acid having a C4 to C20 alkyl or alkenyl group, or an ester of polyethylene glycol (3 to 40 moles) with the above carboxylic acid;
polypropylene glycol carboxylic acid ester which is an adduct of 3 to 40 moles of propylene oxide with a carboxylic acid having a C4 to C20 alkyl or alkenyl group, or an ester of polypropylene glycol (3 to 40 6~'Z
moles) with the above carboxylic acid;
polyoxypropylene-polyoxyethylene carboxylic acid ester which is an adduct of 3 to 40 moles of a mixture of propylene oxide and ethylene oxide with a carboxylic acid having a C4 to C20 alkyl or alkenyl group, or an ester of polyoxypropylene-polyoxyethylene diol (3 to 40 moles) with the above carboxylic acid;
polyoxyethylene alkyl- or alkylene-amine which is an adduct of 3 to 40 moles of ethylene oxide with an alkyl-or alkylene-amine having a C~ to C20 alkyl or alkylene group;
polyoxypropylene alkyl- or alkylene-amine which is an adduct of 3 to 40 moles of propylene oxide with an alkyl-or alkylene-amine'having a C6 to C20 alkyl or alkylene group;
polyoxypropylene-polyoxyethylene alkyl- or alkylene-amine which is an adduct of 3 to 40 moles of a mixture of propylene oxide and ethylene oxide with an alkyl- or alkylene-amine having a C6 to C20 alkyl or alkylene group;
adduct of 3 to 40 moles of ethylene oxide with an alkyl mercaptan having a C6 to C20 alkyl group;
adduct of 3 to 40 moles of propylene oxide with an alkyl mercaptan having C6 to C20 alkyl group;
adduct of 3 to 40 moles of a mixture of propylene oxide and ethylene oxide with an alkyl mercaptan having a C6 to C20 alkyl group;
adduct of 3 to 40 moles of ethylene oxide with a reaction product of a carboxylic acid having a C4 to C20 alkyl or 30 alkenyl group and an alkanolamine;
adduct of 3 to 40 moles of propylene oxide with a reaction product of a carboxylic acid having a C4 to C20 alkyl or alkenyl group and an alkanolamine;
adduct of 3 to 40 moles of a mixture of propylene oxide 35 and ethylene oxide with a reaction product of a carboxylic acid having a C4 to C20 alkyl or alkenyl group and an alkanolamine;
adduct having a molecular weight of at most I,000 of at ~,25~6~
least 3 moles of ethylene oxide with a polyhydric alcohol, a polycarboxylic acid, a polyamine, a polyhydric phenol, or their derivatives;
adduct having a molecular weight of at most l,000 of at least 3 moleq of propylene oxide with a polyhydric alcohol, a polycarboxylic acid, a polyamine, a polyhydric phenol, or their derivatives;
adduct having a molecular weight of at most l,000 of at least 3 moles of a mixture of ethylene oxide and propylene oxide with a polyhydric alcohol, a polycarboxylic acid, a polyamine, a polyhydric phenol, or their derivatives;
adduct having a molecular weight of at most 5,000 of at least 3 moles of ethylene oxide with an ester of castor oil or lanoline having hydroxyl group;
adduct having a molecular weight of at most 5,000 of at least 3 moles of propylene oxide with an ester of castor oil or lanoline having hydroxyl group;
adduct having a molecular weight of at most 5,000 of at least 3 moles of a mixture of ethylene oxide and propylene oxide with an ester of castor oil or lanoline having hydroxyl group; and ether of polyethylene glycol, polypropylene glycol or polyoxyethylene-polyoxypropylene copolymer. In particular, there are preferred adducts of 3 to 40 moles, especially lO to 25 moles, of ethylene oxide with an alkylphenol or aralkylphenol having a C4 ro C28 alkyl or aralkyl group, especially a Cl4 to C20 alkyl or aralkyl group (polyoxyethylene alkylphenyl or aralkylphenyl ethers).
The non-ionic surface active agent having terminal tertiary hydroxyl group has no or little reactivity to the substituted succinic anhydride (I) and, therefore, even if the both are mixed and sto~ed for a long term, the initial emulsifiability can be maintained.
Also, a conventionally used expensive emulsification equipment is not required, and it is possible to prepare an aqueous emulsion by using a simple agitating apparatus.
The non-ionic surface active agent having terminal tertiary hydroxyl group is used in an amount of 1 to 25 ~ by weight, preferably 3 to 20 ~ by weight, based on the substituted succinic anhydride (I). When the amount is less than 1 % by weight, the compound (I) is not suf~iciently emulsified, and when the amount is more than 25 ~ by weight, an emulsion of good state is obtained, but the sizing effect is remarkably lowered.
The non-ionic surface active agent having terminal tertiary hydroxyl group may be employed in combination with anionic surface active agents, other non-ionic surface active agents, and/or cationi~ed starch as an emulsifier`for emulsifying the substituted succinic anhydride.
The paper sizing agent of the present invention can be formed into an aqueous emulsion in a usual manner.
For instance, the substituted ~uccinic anhydride (I) and emulsifier are uniformly admixed and the mixture is dispersed into water to form an emulsion. Alternatively, the emulsifier is first added to water and the substituted succinic anhydride is then added thereto to form an emulsion. The former method wherein a uniform mixture of the compound (I) and the emulsifier is dispersed into water, is convenient and moreover is adoptable, since the sizing composition of the present invention can maintain the initial emulsifiability even if stored for a long term. According to the present invention, it is also posslble to use a simple agitator such as a propeller mixer, a paddle mixer or a line mixer as a mixing machine for forming an aqueous emulsion.
The sizing agent of the present invention comprising the substituted succinic anhydride (I) and the emulsifier may be used in combination with other known sizing agents for internal sizing of paper such as rosin sizing agents, petroleum sizing agents, wax sizing agents and alkyl ketene dimer sizing agent, as occasion demands.
The use of a Eixing agent is effective for increasing the retention of the sizing agent. Cationized starch and cationic polymers are preferably used as a fixing agent. Examples of the cationic polymers are, for instance, polyaminepolyamide-epihalohydrin, polyvinyl pyridine and quaternary salts thereof, cyclopolymerization products of halogenated diallyl, and various cationized polyacrylamides.
In paper making, the sizing agent of the present invention is used in an amount of 0.01 to 4 % by weight, preferably 0.05 to 2 ~ by weight, as solid matter based on pulp.
The fixing agent can be added to a pulp slurry simultaneously with, before or after adding the sizing agent, but the addition after adding the sizing agent is preferred.
Wet paper sheets or webs obtained by adding the sizing agent to an aqueous pulp slurry and forming the pulp into sheets or webs are dried usually at a temperature of 80 to 140C.
The present invention is more specifically described and explained by means o the following Examples, in which all % and parts are by weight unless otherwise noted. It is to be understood that the present invention is not limited to the Examples, and various changes and modifications may be made in the invention without departing ~rom the spirit and scope thereof.
Examples 1 to 14 and Comparative Examples 1 and 2 An alkenyl succinic anhydride prepared by reaction of a linear internal olefin having 14 to 18 carbon atoms and maleic anhydride was uniformly admixed with, as an emulsifier, each of the non-ionic surface active agents having terminal tertiary hydroxyl group prepared by addition reaction of non~ionic surface active agents and isobutylene oxide (IBO) or ~-methylstyrene oxide (MSO), and the non-ionic surface active agents having no terminal tertiary hydroxyl group shown in Table 1. ~
~2~ Z.
The resulting mixture ~sizing agent) was subjected to infrared spectrophotometry to observe the presence of ester absorption in the vicinity of l,730 cm 1 immediately after preparing-the mixture and after allowing the mixture to stand at 50C for 1 month.
The results are shown in Table 1.
Also, the mixture was uniformly dispersed into a predetermined amount of water to form an aqueous emulsion containing the alkenyl succinic anhydride in a concentration of 0.5 ~. The emulsion was added to a pulp slurry so that the amount of the sizing agent (as solid matters) was 0.2 ~ on a dry pulp basis, and the pulp was formed into a sheet. The degree of sizing was measured by a Stoeckight method according to Japanese Industrial Standard (JIS) P-8122.
With respect to the mixture (sizing agent) allowed to stand at 50C for 1 month, the above procedures were repeated.
The results are shown in Table 2.
The conditions of paper making were as shown below.
Pulp: LBKP
Basis weight: 70 y/m2 Filler: calcium carbonate (20 % on a dry pulp basis) Fixing agent: cationized starch Drying: rotary drier (105C, 3 minutes) Paper machine: TAPPI standard paper machine .Ec oo : = ~ = ~ = = ~ ~
h o Z
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o ~ ~ m _ ~
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m O o~
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X X X XO X O X Z
~ 1 1.25~6~
~ 12 Table 2 Stoeckight sizing degree (second) Just after mixing After 1 month at 50C
Ex. 1 32 32 Ex. 2 31. 31 Ex. 3 30 29 Ex. 4 3]. 31 Ex. 5 29 28 Ex. 6 28 27 Ex. 7 30 29 Ex. 8 22 22 Ex. 9 ' 25 23 Ex. 10 30 27 Ex. 11 26 22 Ex. 12 27 25 Ex. 13 31 29 Ex. 14 25 25 Com.
Ex. 1 12 0 Com.
Ex. 2 8 0 ~:~ 25 Examples 15 to 21 and Comparative~Exam~les 3 and 4 The procedures of the preceding Examples were repeated except that the emulsifiers shown in Table 3 were employed.
: The results of measurement of the Stoeckight sizing degree ar~ shown in Table 3 with respect to sizing agents just after the preparation:.
~ a .
X ~
~ c o ~ ~ I`
aJ._, ~, ~ ~
O N QJ
.IJ-~
U~
~ ~ 'O
U~
Q ~
0~ rl U~ ,( C
~ U7 U
O C~
~0 a a Q m (1~ H 4~
E-l ~ _ ,~ V
^ ~ ~ (I) _ ,_ .
_ O
a o m ~ ~ c o o o ,~
~ P~ a) H OD ~`1 0 m ~n o ~ ~ ~ ~, -- 4-1 a) H `~ O
4~ O ~ IJ ~ ~ -- ~
^ r~l ~ O;~ O ~ U~ l O ~
~ U? ~ ~.) `~ ~ ~ ~ 11-1 Ql ~--1 r--l ~ Ul o o c~ O ~ o -- ~ o m ~ ~ o ~n a) 0~ c o o o o ~ a) ~ ~
Ll H C ~ U~ ~(~ ~ -IJ ~1 ~ ~n 5~ ~ c a) ~ ~ 1 o ^ o ~ ~ -- N
~1 ~ N 0 ~1 ~ ~ U -- ~ O S:~ ~ ~ -- 0 N O ~
~1 O C C ~1 ~ CO r~ 1 a) -- -- o o C -- Ç 1~ ~ 1 ,~ ~`I a) aJ :~ o ~ 1 ~ ~ o oc~ ~ ~1 a~ r-- (1) O ~ ~ ~ O ~ O O ~ -- O O O ~ O ~ O
~5 ~ ~ l 5 U O 1 ~ ~ ~ ~ ~ o ~ a) ~ ~ o o ~ ~ ~ ~ ~ ~ u o :~
1:~ ~1 0 O) UC ~1 ~1 .--1 ~ U ~ ~ ~1 ~1 ~1 0 ~1 0 U h . o ~ -1~ oa) o o o ~ o ~ o o IJ O
C O r~ 1C ~ C n~ c o (~5 a) ~ c ~ 3 a) ~j aJ ~1 U a) a) O ~ O ~ ~1 s a) ~1 c ~ c ~I E~ ,a .c c c a~ c ~1 :1 C ~ C ~ ~ 1 U ~ ~ .
~ O ~ O ~-~ ~ U ~
c ~ ~n ~ C c~ C ~
O O ~( O ~1 0 ~ U O ~ ~ ~ O O ~ 1 0 0 ~ O
z rn a ~n C~ Z ~ o ~n ~n c~ o æ Z m ~ z ~n ~n ~n U~ O ~
X X X X X X X Eo X E .
~2s~
It is observed in Tables 1 and 2 that the sizing agent of the present invention has an excellent sizing effect.
Examples 22 to 30 An aqueous emulsion was prepared by adding 100 parts of the same alkenylsuccinic anhydride as used in Examples 1 to 14 and 5 parts of the emulsifier shown in Table 4 to 2,000 parts of water at one time.
Using the thus prepared emulsion, a paper was formed and the Stoeckight sizing degree thereof was measured in the same manner as in Examples l to 14.
The results are shown in Table 4.
~Z$~6~
N 'O
t~ ~
J
U~
., 1 o o~ ~ o a~ 1` ~
~ a) ~ ~ ~ ~ ~ ~ ~ ~ ~ D7 O ~ .~
U~ lU
O
. 3 O
~ a) : o a~ ~ ~: .~
~ O
R ~ ~ ; Q~ a) a~ H O C _I O O ~ u~ .C
El ~ a~ 0 _ H t'`l 4-1 O ~ ~
_ ~ ~ ~ _ ~ ~ ~ -- Qi ~1 -- O ~ t`J : _ _ O O
~ ~ O ~-- o o O ~ -- ~1 O -- H: ^ E~:l O t~ ~ O
~ o ~ a) u~ ~a :: : L~: ~ ~ ~ 'O O ~I C) ---- ~:
~ ~ O ~ ~ ~ O ui o O
, 1 O -- ~I N O C -- ~ ~ C 5~ ,~
~:: o -- c ~ aJ o _ a~ --~,~ ~ ~ O
u~ .~ 0 C2~ O ~ ~1 O ~ O O ~ -~ ~ ~~ ~ ~
:~ ~ ~ ~, C ~, 1~ ~ C~ O~ S
o ~ a) c ~ ~ aJ a) ~ o ~il a) ~ t~ a) ~:: o ~ ~ ~ ~ ~ r ,~ .
o o ~ ~ c o ,~~n td a~ ~ a c: ~ ~ 3 c a) ~ ~ ~ ~ a) ~ a) .i Q.
~, a) ~ ~1 N ~ - h :: : h ~ ~ O 0 ~1 a):c ~ ~ c) a) ~'-1 ~ O $~ ~ Q 0 ~ O ~ ~1 ~1 0 ~a) ~ ~ ~3 c ~::1 h --1 a) r~ C~.
.r~ O ~-1 0 ~I Ei O ~: O h r-l 0: h ~ ., a z o u~ ; z; ~ o Q E~ l~i ; : C
~: ~ ~ ~ U~ ~ o ~ 3 ~ ~ ~ ~ ~ ~ ~ a) ... . ... - . O
X X X X X X X X X Z
~ ~ ~ W ~ ~ W ~ ~
.
~1~25~26~
From the results shown in Table 4, it would be understood that even if the substituted succinic anhydride and the emulsifier are separately added without previously forming into a mixture, an excellent sizing effect can be exhibited.
In addition to the ingredients used in the Examples, other ingredients can be used in the Examples as set forth in the specification to obtain substantially the same results~
BACKGROUND OF THE INVENTION
The present invention relates to a sizing agent suitable for use in paper ma~ing, and more particularly to a paper sizing agent comprising a substituted succinic anhydride and an emulsifier, which is capable of exhibiting an excellent sizing effect even after stored for a long term.
Various materials have been used for sizing paper. In recent years, sizing using a dicarboxylic acid anhydride has been proposed.
Dicarboxylic acid anhydrides such as substituted succinic anhydrides, which have been used for sizing paper in neutral pH region, have been used usually in the form of an aqueous emulsion by emulsifying in water using an emulsifier such as a surface active agent or cationized starch and a homogenizer or homomixer. It is known that if the dicarboxylic acid anhydride is previously admixed with an emulsifier and stored in the form of a mixture, the emulsifying ability is lowered in a short term and, therefore, the sizing effect is also lowered.
It is an object of the present invention to provide a paper sizing agent comprising a substituted succinic anhydride and an emulsifierl which can exhibit an excellent sizing effect even after stored for a long term.
The above and other objects of the present invention will become apparent from the description hereinafter.
SUMMARY OF THE INVENTION
It has now been found that when a non-ionic surface active agent having a terminal tertiary hydroxyl group is used as at least one component of the emulsifier for emulsifying a substituted succinic anhydride, an excellent sizing effect is obtained even if they are stored in the form of a mixture for a long term.
The term "terminal tertiary hydroxyl group" as 5~ 2 _ 3 used herein means a terminal hydroxyl group bonding to tertiary carbon, in other words, a tertiary alcohol residue represented by the formula: -I-OH positioned at the molecular end.
In accordance with the present invention, there is provided a sizing agent comprising a substituted succinic anhydride of the formula: (I):
R-C~- C~
10 O=C C=O (I) \0/
wherein R is a hydrocarbon group having at least 6 carbon atoms selected from the group consisting of an alkyl group, an alkenyl group, an aralkyl group or an aralkenyl group, and an emulsifier comprising a non-ionic surface active agent having a terminal tertiary hydroxyl group.
DETAILED DESCRIPTION
In the above substituted succinic anhydrides of the formula (I)~ those having the substituent R which is a C6 to C30 alkyl or alkenyl group, especially a Cl2 to C24 alkyl or alkenyl group are preferred.
Representative examples of the substituted succinic anhydride (I) are, for instance, dodecyl succinic anhydride, n-hexadecyl succinic anhydride, n-octadecenyI
succinic anhydride, isooctadecenyl succinic anhydride, l-methyl-2-pentadecenyl succinic anhydride and l-propyl-2-pentadecenyl succinic anhydride. The substituted succinicanhydrides may be used alone or in admixture thereof.
In the present invention, a non-ionic surface active agent having terminal tertiary hydroxyl group is employed as at least one component of the emulsifier used for emulsifying the compound (I).
The non-ionic surface active agent having terminal tertiary hydroxyl group can be prepared, for instance, by addition reaction of usual non-ionic surface .
S~
active agent and isobutylene oxide or ~-methylstyrene oxide, but the process for the preparation thereof is not limited thereto.
Representative examples of the non-ionic surface active agent used as a raw material in the above reaction are, for instance: ~
polyoxyethylene alkyl ether which is an adduct of 3 to 40 moles of ethylene oxide with an alcohol having a C6 to C20 alkyl group;
polyoxypropylene alkyl ether which is an adduct of 3 to 40 moles of propylene oxide with an alcohol having a C6 to C20 alkyl group;
polyoxypropylene~polyoxyethylene alkyl ether which is an adduct of 3 to 40 moles of a mixture of propylene oxide and ethylene oxide with an alcohol having a C6 to C20 alkyl group;
polyoxyethylene alkylphenyl or aralkylphenyl ether which is an adduct of 3 to 40 moles of ethylene oxide with an alkylphenol or aralkylphenol having a C4 to C28 alkyl or aralkyl group;
polyoxypropylene alkylphenyl or aralkylphenyl ether which is an adduct of 3 to 40 moles of propylene oxide with an alkylphenol or aralkylphenol having a C4 to C28 alkyl or aralkyl group;
polyoxyethylene-polyoxypropylene alkylphenyl or aralkylphenyl ether which is an adduct or 3 to 40 moles of a mixture of ethylene oxide and propylene oxide with an alkylphenol or aralkylphenol having a C4 to C28 alkyl or aralkyl group;
polyethylene glycol carboxylic acid ester which is an adduct of 3 to 40 moles of ethylene oxide with a carboxylic acid having a C4 to C20 alkyl or alkenyl group, or an ester of polyethylene glycol (3 to 40 moles) with the above carboxylic acid;
polypropylene glycol carboxylic acid ester which is an adduct of 3 to 40 moles of propylene oxide with a carboxylic acid having a C4 to C20 alkyl or alkenyl group, or an ester of polypropylene glycol (3 to 40 6~'Z
moles) with the above carboxylic acid;
polyoxypropylene-polyoxyethylene carboxylic acid ester which is an adduct of 3 to 40 moles of a mixture of propylene oxide and ethylene oxide with a carboxylic acid having a C4 to C20 alkyl or alkenyl group, or an ester of polyoxypropylene-polyoxyethylene diol (3 to 40 moles) with the above carboxylic acid;
polyoxyethylene alkyl- or alkylene-amine which is an adduct of 3 to 40 moles of ethylene oxide with an alkyl-or alkylene-amine having a C~ to C20 alkyl or alkylene group;
polyoxypropylene alkyl- or alkylene-amine which is an adduct of 3 to 40 moles of propylene oxide with an alkyl-or alkylene-amine'having a C6 to C20 alkyl or alkylene group;
polyoxypropylene-polyoxyethylene alkyl- or alkylene-amine which is an adduct of 3 to 40 moles of a mixture of propylene oxide and ethylene oxide with an alkyl- or alkylene-amine having a C6 to C20 alkyl or alkylene group;
adduct of 3 to 40 moles of ethylene oxide with an alkyl mercaptan having a C6 to C20 alkyl group;
adduct of 3 to 40 moles of propylene oxide with an alkyl mercaptan having C6 to C20 alkyl group;
adduct of 3 to 40 moles of a mixture of propylene oxide and ethylene oxide with an alkyl mercaptan having a C6 to C20 alkyl group;
adduct of 3 to 40 moles of ethylene oxide with a reaction product of a carboxylic acid having a C4 to C20 alkyl or 30 alkenyl group and an alkanolamine;
adduct of 3 to 40 moles of propylene oxide with a reaction product of a carboxylic acid having a C4 to C20 alkyl or alkenyl group and an alkanolamine;
adduct of 3 to 40 moles of a mixture of propylene oxide 35 and ethylene oxide with a reaction product of a carboxylic acid having a C4 to C20 alkyl or alkenyl group and an alkanolamine;
adduct having a molecular weight of at most I,000 of at ~,25~6~
least 3 moles of ethylene oxide with a polyhydric alcohol, a polycarboxylic acid, a polyamine, a polyhydric phenol, or their derivatives;
adduct having a molecular weight of at most l,000 of at least 3 moleq of propylene oxide with a polyhydric alcohol, a polycarboxylic acid, a polyamine, a polyhydric phenol, or their derivatives;
adduct having a molecular weight of at most l,000 of at least 3 moles of a mixture of ethylene oxide and propylene oxide with a polyhydric alcohol, a polycarboxylic acid, a polyamine, a polyhydric phenol, or their derivatives;
adduct having a molecular weight of at most 5,000 of at least 3 moles of ethylene oxide with an ester of castor oil or lanoline having hydroxyl group;
adduct having a molecular weight of at most 5,000 of at least 3 moles of propylene oxide with an ester of castor oil or lanoline having hydroxyl group;
adduct having a molecular weight of at most 5,000 of at least 3 moles of a mixture of ethylene oxide and propylene oxide with an ester of castor oil or lanoline having hydroxyl group; and ether of polyethylene glycol, polypropylene glycol or polyoxyethylene-polyoxypropylene copolymer. In particular, there are preferred adducts of 3 to 40 moles, especially lO to 25 moles, of ethylene oxide with an alkylphenol or aralkylphenol having a C4 ro C28 alkyl or aralkyl group, especially a Cl4 to C20 alkyl or aralkyl group (polyoxyethylene alkylphenyl or aralkylphenyl ethers).
The non-ionic surface active agent having terminal tertiary hydroxyl group has no or little reactivity to the substituted succinic anhydride (I) and, therefore, even if the both are mixed and sto~ed for a long term, the initial emulsifiability can be maintained.
Also, a conventionally used expensive emulsification equipment is not required, and it is possible to prepare an aqueous emulsion by using a simple agitating apparatus.
The non-ionic surface active agent having terminal tertiary hydroxyl group is used in an amount of 1 to 25 ~ by weight, preferably 3 to 20 ~ by weight, based on the substituted succinic anhydride (I). When the amount is less than 1 % by weight, the compound (I) is not suf~iciently emulsified, and when the amount is more than 25 ~ by weight, an emulsion of good state is obtained, but the sizing effect is remarkably lowered.
The non-ionic surface active agent having terminal tertiary hydroxyl group may be employed in combination with anionic surface active agents, other non-ionic surface active agents, and/or cationi~ed starch as an emulsifier`for emulsifying the substituted succinic anhydride.
The paper sizing agent of the present invention can be formed into an aqueous emulsion in a usual manner.
For instance, the substituted ~uccinic anhydride (I) and emulsifier are uniformly admixed and the mixture is dispersed into water to form an emulsion. Alternatively, the emulsifier is first added to water and the substituted succinic anhydride is then added thereto to form an emulsion. The former method wherein a uniform mixture of the compound (I) and the emulsifier is dispersed into water, is convenient and moreover is adoptable, since the sizing composition of the present invention can maintain the initial emulsifiability even if stored for a long term. According to the present invention, it is also posslble to use a simple agitator such as a propeller mixer, a paddle mixer or a line mixer as a mixing machine for forming an aqueous emulsion.
The sizing agent of the present invention comprising the substituted succinic anhydride (I) and the emulsifier may be used in combination with other known sizing agents for internal sizing of paper such as rosin sizing agents, petroleum sizing agents, wax sizing agents and alkyl ketene dimer sizing agent, as occasion demands.
The use of a Eixing agent is effective for increasing the retention of the sizing agent. Cationized starch and cationic polymers are preferably used as a fixing agent. Examples of the cationic polymers are, for instance, polyaminepolyamide-epihalohydrin, polyvinyl pyridine and quaternary salts thereof, cyclopolymerization products of halogenated diallyl, and various cationized polyacrylamides.
In paper making, the sizing agent of the present invention is used in an amount of 0.01 to 4 % by weight, preferably 0.05 to 2 ~ by weight, as solid matter based on pulp.
The fixing agent can be added to a pulp slurry simultaneously with, before or after adding the sizing agent, but the addition after adding the sizing agent is preferred.
Wet paper sheets or webs obtained by adding the sizing agent to an aqueous pulp slurry and forming the pulp into sheets or webs are dried usually at a temperature of 80 to 140C.
The present invention is more specifically described and explained by means o the following Examples, in which all % and parts are by weight unless otherwise noted. It is to be understood that the present invention is not limited to the Examples, and various changes and modifications may be made in the invention without departing ~rom the spirit and scope thereof.
Examples 1 to 14 and Comparative Examples 1 and 2 An alkenyl succinic anhydride prepared by reaction of a linear internal olefin having 14 to 18 carbon atoms and maleic anhydride was uniformly admixed with, as an emulsifier, each of the non-ionic surface active agents having terminal tertiary hydroxyl group prepared by addition reaction of non~ionic surface active agents and isobutylene oxide (IBO) or ~-methylstyrene oxide (MSO), and the non-ionic surface active agents having no terminal tertiary hydroxyl group shown in Table 1. ~
~2~ Z.
The resulting mixture ~sizing agent) was subjected to infrared spectrophotometry to observe the presence of ester absorption in the vicinity of l,730 cm 1 immediately after preparing-the mixture and after allowing the mixture to stand at 50C for 1 month.
The results are shown in Table 1.
Also, the mixture was uniformly dispersed into a predetermined amount of water to form an aqueous emulsion containing the alkenyl succinic anhydride in a concentration of 0.5 ~. The emulsion was added to a pulp slurry so that the amount of the sizing agent (as solid matters) was 0.2 ~ on a dry pulp basis, and the pulp was formed into a sheet. The degree of sizing was measured by a Stoeckight method according to Japanese Industrial Standard (JIS) P-8122.
With respect to the mixture (sizing agent) allowed to stand at 50C for 1 month, the above procedures were repeated.
The results are shown in Table 2.
The conditions of paper making were as shown below.
Pulp: LBKP
Basis weight: 70 y/m2 Filler: calcium carbonate (20 % on a dry pulp basis) Fixing agent: cationized starch Drying: rotary drier (105C, 3 minutes) Paper machine: TAPPI standard paper machine .Ec oo : = ~ = ~ = = ~ ~
h o Z
ta o o c ~1~ O
O
. h h O ~ ~ C
Q ~ C 0 ~ X
~ .
ra '~
u~
~ ~ e - = ~ = c Q ~ r~
o\ A
U~ ._1 Q c C ~ 1 _ O ~
o ~ ~ m _ ~
~ o E~ ~ ---- -- H 0~ --O --O ^ ~ O ~ ~ O
m O o~
u, m ~ C~ O _ ~ ~ In ^ ~ m -- ~3 o ~ ~
_ _ In -- H ~--I -- ~ ~ --~ ~ o ~ ~ o o: c m h r~ ~ H ~ ~ S ~1 a) o ~ ^ u~ ~ o .~ s:: ~ O ~ O -- 117 ~ G) ~ ~ O ~ ~ ~ ~ O ~
, ~ ~ S
U~ ~ -- O ~ ~ `- O ~ O
O ~ ~ O O ~ ~ ~
::5 ~ 1 ~ O S j~il ~ h 'a E~ o ~ ~I C O ~ a~
o a U
~1) ac~ u~ C~
h h ~ ~ ,-1 r-l a,) U h J~ ~ o ~ .,U, ~ ~o u~ ~ C ~ aJ 3 1 0 ~
a u z a ~ o ~ c ~ a .~ X X X ~c X X X X X
[~ ~ ~ ~
~zs~
~::
o a a~ c c a) o c ~ a =
u~ ~ u~ Z ~ a~
Q) ~1 ~ h C f~
O O
~ 4, O
u~ c a Q ~ ,1 C
f:l Ul X O -1~'~ Z
a) .
U~
R ::~ C
d~ :~
_ U~,l ~ - e _ VQ C
C ~-,1 U~
o u~ o a) ~0~ ~ ~o 4_1 ~ o ~1 ~ _ O : ~ Q
~1 ~ ~ a) ~ c -- ~ O ~ _ _~ a) o o ~ o o ~ a~
:: ~: ~ O ~ O
~ ~ ~ O IQ
a) o 1` ^ ^ ~ a a) ~ ~ v ~ ~ ~
~J -- ~ a) ~ c ~
~1 O ~ 1 0 0 3 a) ~5 0 QJ ~C
.-1 1~ ~1~ W ~ ~
tQ ~ I O~ ~ ~ ~ rl X ~ ~ C
oa~ ~ ~ ~ ~ o o JJ ~ O O O
c v o~ In C
o ~ ~ ~ I` a) o . ~ ~ S ~) C ~ ~ S
~1 C~ ~ ~ ~ ~ ~ ~ C
a c~ o ~ ~ ~ 'I ~ ~ a) ,, ~ S ~ ~ ~ O
~ Q~ ~ C ~ ~ O
O Q~ --I O ~ ~ 1-1 H ~ (~
~:5 aJ CL
a) ,~ O0 3 ~ ~ .. .- a) ~ o ~ o O O m a ~1 ~ ~ H ~ Z
V
C
O ~ ~ ~ ~ ~ ~
. . . - ~ O
X X X XO X O X Z
~ 1 1.25~6~
~ 12 Table 2 Stoeckight sizing degree (second) Just after mixing After 1 month at 50C
Ex. 1 32 32 Ex. 2 31. 31 Ex. 3 30 29 Ex. 4 3]. 31 Ex. 5 29 28 Ex. 6 28 27 Ex. 7 30 29 Ex. 8 22 22 Ex. 9 ' 25 23 Ex. 10 30 27 Ex. 11 26 22 Ex. 12 27 25 Ex. 13 31 29 Ex. 14 25 25 Com.
Ex. 1 12 0 Com.
Ex. 2 8 0 ~:~ 25 Examples 15 to 21 and Comparative~Exam~les 3 and 4 The procedures of the preceding Examples were repeated except that the emulsifiers shown in Table 3 were employed.
: The results of measurement of the Stoeckight sizing degree ar~ shown in Table 3 with respect to sizing agents just after the preparation:.
~ a .
X ~
~ c o ~ ~ I`
aJ._, ~, ~ ~
O N QJ
.IJ-~
U~
~ ~ 'O
U~
Q ~
0~ rl U~ ,( C
~ U7 U
O C~
~0 a a Q m (1~ H 4~
E-l ~ _ ,~ V
^ ~ ~ (I) _ ,_ .
_ O
a o m ~ ~ c o o o ,~
~ P~ a) H OD ~`1 0 m ~n o ~ ~ ~ ~, -- 4-1 a) H `~ O
4~ O ~ IJ ~ ~ -- ~
^ r~l ~ O;~ O ~ U~ l O ~
~ U? ~ ~.) `~ ~ ~ ~ 11-1 Ql ~--1 r--l ~ Ul o o c~ O ~ o -- ~ o m ~ ~ o ~n a) 0~ c o o o o ~ a) ~ ~
Ll H C ~ U~ ~(~ ~ -IJ ~1 ~ ~n 5~ ~ c a) ~ ~ 1 o ^ o ~ ~ -- N
~1 ~ N 0 ~1 ~ ~ U -- ~ O S:~ ~ ~ -- 0 N O ~
~1 O C C ~1 ~ CO r~ 1 a) -- -- o o C -- Ç 1~ ~ 1 ,~ ~`I a) aJ :~ o ~ 1 ~ ~ o oc~ ~ ~1 a~ r-- (1) O ~ ~ ~ O ~ O O ~ -- O O O ~ O ~ O
~5 ~ ~ l 5 U O 1 ~ ~ ~ ~ ~ o ~ a) ~ ~ o o ~ ~ ~ ~ ~ ~ u o :~
1:~ ~1 0 O) UC ~1 ~1 .--1 ~ U ~ ~ ~1 ~1 ~1 0 ~1 0 U h . o ~ -1~ oa) o o o ~ o ~ o o IJ O
C O r~ 1C ~ C n~ c o (~5 a) ~ c ~ 3 a) ~j aJ ~1 U a) a) O ~ O ~ ~1 s a) ~1 c ~ c ~I E~ ,a .c c c a~ c ~1 :1 C ~ C ~ ~ 1 U ~ ~ .
~ O ~ O ~-~ ~ U ~
c ~ ~n ~ C c~ C ~
O O ~( O ~1 0 ~ U O ~ ~ ~ O O ~ 1 0 0 ~ O
z rn a ~n C~ Z ~ o ~n ~n c~ o æ Z m ~ z ~n ~n ~n U~ O ~
X X X X X X X Eo X E .
~2s~
It is observed in Tables 1 and 2 that the sizing agent of the present invention has an excellent sizing effect.
Examples 22 to 30 An aqueous emulsion was prepared by adding 100 parts of the same alkenylsuccinic anhydride as used in Examples 1 to 14 and 5 parts of the emulsifier shown in Table 4 to 2,000 parts of water at one time.
Using the thus prepared emulsion, a paper was formed and the Stoeckight sizing degree thereof was measured in the same manner as in Examples l to 14.
The results are shown in Table 4.
~Z$~6~
N 'O
t~ ~
J
U~
., 1 o o~ ~ o a~ 1` ~
~ a) ~ ~ ~ ~ ~ ~ ~ ~ ~ D7 O ~ .~
U~ lU
O
. 3 O
~ a) : o a~ ~ ~: .~
~ O
R ~ ~ ; Q~ a) a~ H O C _I O O ~ u~ .C
El ~ a~ 0 _ H t'`l 4-1 O ~ ~
_ ~ ~ ~ _ ~ ~ ~ -- Qi ~1 -- O ~ t`J : _ _ O O
~ ~ O ~-- o o O ~ -- ~1 O -- H: ^ E~:l O t~ ~ O
~ o ~ a) u~ ~a :: : L~: ~ ~ ~ 'O O ~I C) ---- ~:
~ ~ O ~ ~ ~ O ui o O
, 1 O -- ~I N O C -- ~ ~ C 5~ ,~
~:: o -- c ~ aJ o _ a~ --~,~ ~ ~ O
u~ .~ 0 C2~ O ~ ~1 O ~ O O ~ -~ ~ ~~ ~ ~
:~ ~ ~ ~, C ~, 1~ ~ C~ O~ S
o ~ a) c ~ ~ aJ a) ~ o ~il a) ~ t~ a) ~:: o ~ ~ ~ ~ ~ r ,~ .
o o ~ ~ c o ,~~n td a~ ~ a c: ~ ~ 3 c a) ~ ~ ~ ~ a) ~ a) .i Q.
~, a) ~ ~1 N ~ - h :: : h ~ ~ O 0 ~1 a):c ~ ~ c) a) ~'-1 ~ O $~ ~ Q 0 ~ O ~ ~1 ~1 0 ~a) ~ ~ ~3 c ~::1 h --1 a) r~ C~.
.r~ O ~-1 0 ~I Ei O ~: O h r-l 0: h ~ ., a z o u~ ; z; ~ o Q E~ l~i ; : C
~: ~ ~ ~ U~ ~ o ~ 3 ~ ~ ~ ~ ~ ~ ~ a) ... . ... - . O
X X X X X X X X X Z
~ ~ ~ W ~ ~ W ~ ~
.
~1~25~26~
From the results shown in Table 4, it would be understood that even if the substituted succinic anhydride and the emulsifier are separately added without previously forming into a mixture, an excellent sizing effect can be exhibited.
In addition to the ingredients used in the Examples, other ingredients can be used in the Examples as set forth in the specification to obtain substantially the same results~
Claims (10)
1. A sizing agent comprising a substituted succinic anhydride of the formula (I):
(I) wherein R is a hydrocarbon group having at least 6 carbon atoms selected from the group consisting of an alkyl group, an alkenyl group, an aralkyl group or an aralkenyl group, and an emulsifier comprising a non-ionic surface active agent having a terminal tertiary hydroxyl group.
(I) wherein R is a hydrocarbon group having at least 6 carbon atoms selected from the group consisting of an alkyl group, an alkenyl group, an aralkyl group or an aralkenyl group, and an emulsifier comprising a non-ionic surface active agent having a terminal tertiary hydroxyl group.
2. The sizing agent of Claim 1, wherein said non-ionic surface active agent having a terminal tertiary hydroxyl group is a polyoxyalkylene compound.
3. The sizing agent of Claim 1, wherein said non-ionic surface active agent having a terminal tertiary hydroxyl group is a polyoxyalkylene compound having a terminal group derived from isobutylene oxide.
4. The sizing agent of Claim 1, wherein said non-ionic surface active agent having a terminal tertiary hydroxyl group is a polyoxyalkylene compound having a terminal group derived from .alpha.-methylstyrene oxide.
5. The sizing agent of Claim 1, wherein said non-ionic surface active agent having a terminal tertiary hydroxyl group is an addition reaction product of isobutylene oxide or .alpha.-methylstyrene oxide and a polyoxyethylene alkylphenyl or aralkylphenyl ether.
6. The sizing agent of Claim 5, wherein said polyoxyethylene alkylphenyl or aralkylphenyl ether is an adduct of 3 to 40 moles of ethylene oxide and 1 mole of an alkyl- or aralkyl-phenol having a C4 to C28 alkyl or aralkyl group.
7. The sizing agent of Claim 5, wherein said polyoxyethylene alkylphenyl or aralkylphenyl ether is an adduct of 10 to 25 moles of ethylene oxide and 1 mole of an alkyl- or aralkyl-phenol having a C14 to C20 alkyl or aralkyl group.
8. The sizing agent of Claim 1, wherein the amount of said non-ionic surface active agent having terminal tertiary hydroxyl group is from 1 to 25 % by weight based on said substituted succinic anhydride.
9. The sizing agent of Claim 1, wherein the amount of said non-ionic surface active agent having terminal tertiary hydroxyl group is from 3 to 20 % by weight based on said substituted succinic anhydride.
10. The sizing agent of Claim 1, wherein said emulsifier further contains at least one member selected from the group consisting of anionic surface active agents, other non-ionic surface active agents having no terminal tertiary hydroxyl group and cationized starch.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA000503137A CA1252602A (en) | 1986-03-03 | 1986-03-03 | Sizing agent suitable for use in paper making |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA000503137A CA1252602A (en) | 1986-03-03 | 1986-03-03 | Sizing agent suitable for use in paper making |
Publications (1)
Publication Number | Publication Date |
---|---|
CA1252602A true CA1252602A (en) | 1989-04-18 |
Family
ID=4132591
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA000503137A Expired CA1252602A (en) | 1986-03-03 | 1986-03-03 | Sizing agent suitable for use in paper making |
Country Status (1)
Country | Link |
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CA (1) | CA1252602A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114892440A (en) * | 2022-05-15 | 2022-08-12 | 成都奥睿尔科技创新服务有限公司 | Special glue applying powder for packaging paper |
-
1986
- 1986-03-03 CA CA000503137A patent/CA1252602A/en not_active Expired
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114892440A (en) * | 2022-05-15 | 2022-08-12 | 成都奥睿尔科技创新服务有限公司 | Special glue applying powder for packaging paper |
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