CN1145683C - Clouring adhesive composition for laminated paper product and production method for same - Google Patents

Abstract

An adhesive composition that is suitable for laminating absorbent paper products and paper products laminated using the adhesive composition are disclosed. The adhesive composition provides wet bond strength and a visual signal that desirable properties are maintained when the absorbent paper product becomes wet. The adhesive composition includes a water soluble or dispersible dry strength binder, a water soluble cationic wet strength resin, and a pigment. Also disclosed is a method of producing the adhesive composition. The method includes as an essential step, providing energizing means that can transfer at least about 5 watts per kilogram of power to a resin solution or dispersion as a pigment dispersion is added.

Description

Be used for the colored adhesive composition of laminated thin page or leaf paper product and be used to produce these method for compositions

Invention field

The present invention relates to be used for the binder composition of laminated multilayer cellulosic fibrous structure such as tissue paper product, the thin-paged paper products of producing the method for these binder compositions and using these adhesive composition layer to press.

Background of the present invention

Paper product is known in the daily life.The paper product of some kind is called tissue paper, can be used as paper handkerchief, facial tissue and bath paper.

The tissue paper product can only contain one deck, but contain two-layer or multilayer usually." layer (ply) " used herein is meant independent one deck of peeling off from forming net or its suitable thing, and not dry under the situation that wherein adds other fiber.

Certainly, in each layer, available different types of fiber comes layering.Stratified benefit is that central core can contain tough relatively fiber to give tissue paper product intensity.The skin of central core can be short fiber, gives the user with flexible touch.Layering can be according to the USP3 of common transfer, 994,771 (authorizing people such as Morgan, Jr. on November 30th, 1976) and advantageously finishing, and this patent is incorporated herein as a reference.

Usually, two-layer or multilayer are linked together preparation paper product.The benefit that multilayer is linked together is that the modulus in flexure of gained laminate is lower than the individual layer of same thickness.In addition, its benefit is that also the user can feel a kind of flexible touch.Absorptivity and thickness also increase usually.And, make laminate have different central core and outer three layers of paper product that links together so that intensity and flexibility to be provided respectively.

Multi-layered tissue paper product are cellulosic materials normally.Here used " cellulosic materials " refers to a kind of paper product, it contains at least about 50% weight or at least about the cellulosic fibre of 50% volume, include, but is not limited to velveteen, regenerated fiber, bagasse, more preferably wood pulp, as cork (gymnosperm or softwood tree) or hardwood (angiosperm or deciduous tree), these fibers can reclaim again.Other fiber can be synthon, as polyolefine or polyester.

Cellulose layer uses absorbent core but separated usually.The tackiness agent of cellulose layer is connected among the USP 5,143,776 (authorizing Givens on September 1st, 1992) of common transfer and has done favourable narration, and this patent is incorporated herein by reference.

But, a plurality of layer of fibers in the paper product are connected possibility and have produced not satisfied performance with tackiness agent.Particularly, the paper product as paper handkerchief, facial tissue and bath paper must have suitable laminated intensity (ply bond strength).Here used " laminated intensity " refer to, and is as described below with two adjacent layerss required power that is separated from each other.

Thin paper product, particularly paper handkerchief, wetted in use.If wet laminated undercapacity, then each layer separates in use, thereby destroyed paper product.Although the simple laminated intensity that wets that improves looks that easily it is directly related with wet laminated intensity to do laminated intensity.In the prior art, when wet laminated intensity is brought up to appropriate level, do laminated intensity and will become too big.When dried laminated intensity was too big, flexibility and water-absorbent tended to descend.

The U.S. Patent application sequence number (SN) 08/835039 of common transfer (on March 27th, 1997 is with people's such as Neal name application) discloses can give the nonionic tackiness agent of these glued layers to do laminated intensity and the mixture that the cationic wet strength resins of wet laminated intensity can be provided.Have been found that multilayer paper product that these binder compositions can give adhesive lamination with suitable wet laminated intensity, and can not have too big dried laminated intensity.

Also need the prompting to the user, when paper product was wetting during use, this lamination paper handkerchief can keep its wet laminated intensity.Known in the art, many lamination towel products have the floral designs of aesthetic pleasant, and laminating adhesive then links together these layers at these decorative pattern far-ends.Also known, floral designs disappear when paper handkerchief is wetting.The U.S. Patent application sequence number (SN) 08/749708 of common transfer (the name application of November 15 with people such as Steinhardt in 1996) discloses uses a kind of indicating unit to keep a kind of joyful pattern when paper handkerchief is wetting.Wherein disclosed a kind of indicating unit is to comprise opacifying agent in addition, as the laminating adhesive of titanium dioxide.But common resulting TiO 2 pigment dispersion comprises a kind of anionic polymer toward contact to help prevent these dispersions flocculation and sedimentation takes place.These negatively charged ion stabilising dispersions are made up the visual signalling that the binder composition that obtains also can produce a kind of wet laminated intensity increase with having been found that the cationic wet strength resins that can improve wet laminated intensity.But the uncompatibility of anionic species and cationic substance is well known in the art.

The binder composition that therefore, need also comprise a kind of negatively charged ion stable pigment dispersions with the wet laminated intensity of improved enhanced.Also need negatively charged ion stable pigment dispersions and cationic wet strength resins are mixed into this colored adhesive method for compositions.In addition, also require these colored adhesive compositions to have minimum pigment particles aggregate body and can make the minimized method of this congregation so that the opaque power of these colored adhesive compositions maximizes and needs.

The applicant has been found that the particular composition and the method that can satisfy these requirements just become apparent if with reference to following description and in conjunction with appended embodiment.

Summary of the present invention

The invention provides a kind of being applicable to the laminated binder composition of multi-layer fiber cellulose product.This binder composition comprises the mixture of following material:

(a) the water-soluble or water-dispersible dry strength tackiness agent of about 2-7% weight;

(b) the water-soluble cationic wet-strength resins of about 0.05-5% weight;

(c) the negatively charged ion stable pigments of about 7-30% weight; With

(d) water of about 58-91% weight.

This binder composition preferably adopts and the power supply device that is transferred to this binder composition at least about 5 watts/kilogram can be produced.This transmission can be supplied with the composition produced with enough energy, so that cationic wet strength resins is effectively separated (promptly with the negatively charged ion stable pigments, power supply device can keep a kind of positive charge density effectively), thereby reduced the gathering of granules of pigments and tackiness agent unstable subsequently (as, the cohesion).

Unless refer else, all percentage ratios of the present invention, ratio and ratio all are the weight meters.

The present invention is below described in more detail.

Detailed description of the present invention

Although this specification sheets finishes with the claims that particularly point out and clearly required theme of the present invention,, it is believed that the present invention may be better understood by reading the following detailed description and appended examples.

" comprise " at this term of using and to be meant that various components, composition or step all can be in conjunction with being used to implement the present invention.Therefore, term " comprises " and has comprised that more restrictive term " comprises " substantially and " comprising ".

The present invention includes be suitable for connecting the two-layer or thin page or leaf of multiwalled goods with the colored adhesive composition that increases pigment opacification performance, be used to the paper product producing these method for compositions and use these composition laminations.These layers are as described below to be cellulosic materials, and can make according to identical production method or according to different production methods.

Layer

Every layer can have many embossing, and these embossing are outstanding to adjacent layers from aspect.Adjacent layers can have equally to the outstanding relative projection of the first layer.Three-ply paper product if desired, central core can have outwardly directed embossing on both direction, but central core can not have embossing yet or only has unidirectional embossing.

Each layer can prepare according to the United States Patent (USP) 4,637,859 (authorizing Trokhan on January 20th, 1987) or 4,191,609 (the authorizing Trokhan on March 4th, 1980) of common transfer, and these two patents are incorporated herein as a reference.In addition, these layers can use the described not wrinkleization of european patent application 0617164A1 (on September 28th, 1994 is open), dry air technology (through air dried technology) to make, or using felt to carry out conventional drying, this is known in the art.

At the present invention, every layer quantitatively be about 8～30 pounds/3,000 feet ²(13-48 gram/rice ²), preferred about 11～18 pounds/3,000 feet ²(18-29 gram/rice ²), every layer of hardwood and/or cork composition that preferably has according to any way processing known in the art.

The fiber that constitutes the multilayer paper product is cellulosic materials preferably, and as velveteen, regenerated fiber, bagasse, more preferably wood pulp is as cork (gymnosperm or softwood tree) or hardwood (angiosperm or deciduous tree).If laminated paper product contains at least about 50% weight or at least about the cellulosic fibre of 50% volume, used so here lamination paper product is considered to " cellulosic materials ", includes, but is not limited to above those fibers of enumerating.Other fiber that contains the lamination paper product can be synthon, as polyolefine or polyester.The cellulose mixtures that has been found that a kind of wood pulp cellulose can perform well in lamination paper product described herein, and described wood pulp cellulose comprises the cork fibrous of about 2.0-4.5 millimeter of length and the about 25-50 micron of diameter and the length hardwood fiber less than about 1.7 millimeters and the about 12-25 micron of diameter.

If select wood pulp cellulose to be used for multilayer paper product of the present invention, these fibers can be produced by any pulping process so, comprising chemical method, as sulphite, vitriol and alkaline process; And mechanical process, as the stone mill wood pulp.In addition, chemistry and mechanical means combination also can be prepared fiber, perhaps the method by energy reclaimed waste paper product prepares fiber.The type of used fiber, combination and the course of processing are unimportant for the present invention.Hardwood and cork fibrous can be in the thickness range of whole laminated paper product layering or evenly sneak into wherein.

Binder composition

Each layer use of multilayer paper product links together with binding agent according to the colored adhesive composition of the present invention's preparation.Binder composition preferably is applied in the embossing of one deck at least.Certainly, tackiness agent also can be applied in the two-layer embossing simultaneously.The mixture that comprises dry strength tackiness agent (as, the poly (vinyl alcohol) binder of complete hydrolysis), cationic wet strength resins (as, thermoset resin cation (R.C.)) and negatively charged ion stabilized chlorine titanium slurries according to tackiness agent of the present invention.Particularly preferred binder composition comprises about 58-90 part water, 2-7 part dry strength adhesive solids material, 0.05-5 part cationic wet strength resins solid matter and 7-30 part TiO 2 pigment.Below to describe each in these compounds in detail.

Importantly, in order in finished product laminated thin page or leaf goods of the present invention, to reach gratifying wet and dried laminated intensity and gratifying strength of signal, the binder composition of appropriate amount must be sent on each layer.Suitable transfer approach is discussed in following " lamination flower and lamination " chapters and sections.Each component that adds binder composition with suitable ratio also is important.Those skilled in the art are appreciated that, as long as the adhesive solids material that is sent on each layer is enough to produce gratifying wet and dried laminated intensity and gratifying strength of signal, in the said composition absolute concentration of various solid ingredients can in certain limit, change (as, for the viscosity of control combination thing).Specifically, the ratio of dry strength adhesive solids material and cationic wet strength resins solid matter is important in producing suitable wet laminated intensity within the acceptable range, and it is not too large to do laminated intensity.The ratio of charged solid matter of positively charged ion and the charged solid matter of negatively charged ion also is very important in to obtain having the stable adhesive compositions of enough strength of signal within the acceptable range.

Specifically, the applicant has been found that:

1) ratio of dry strength adhesive solids material and wet-strength resins solid matter should be no more than about 6: 1, can and do between the laminated intensity and reach acceptable balance in wet laminated intensity like this.This ratio is preferably less than about 4: 1.

2) ratio of charged solid matter of negatively charged ion and the charged solid matter of positively charged ion will make the electric density of final binder composition at least about 25 microequivalent/grams (this is that those skilled in the art are intelligible, and concrete weight ratio depends on the electric density of each material).For preferred substance discussed in this article, this means that negatively charged ion charged pigment solid matter (the pigment solids material adds negatively charged ion suspension aids solid matter) should be less than about 40: 1 with positively charged ion solid matter (wet-strength resins solid matter or adding are to keep the charged solid matter of other positively charged ion of clean positive charge density).The ratio of negatively charged ion solid matter and positively charged ion solid matter is preferably less than about 30: 1.This ratio is more preferably less than about 15: 1.

Do strong adhesive material

Binder composition of the present invention comprises about 2-7%, the dried strong adhesive material of preferred 3.5%-6.5% weight is as basal component, be selected from: polyacrylamide (as CyTec Industries of WestPaterson, the Accostrength 711 that N.J. produces); Starch (as RediBOND5320,2005 and 3030E, derives from National Starch and Chemical Company, Bridgewater, New Jersey; Perhaps Amylose 1100,2200 or Salvitose derive from Avebe America, Princeton, New Jersey); Polyvinyl alcohol (as Evanol 71-30, DuPont Corporation ofWilmington, Delaware has supply); And/or guar gum or Viscogum BE.Do strong adhesive material preferably from polyvinyl alcohol, starch-based resin and composition thereof.The effect of doing strong adhesive material is to guarantee that multilayer paper product of the present invention has enough dried laminated intensity.

Binder composition of the present invention, wherein said dry strength adhesive material be selected from polyvinyl alcohol, polyvinyl acetate (PVA), carboxymethyl cellulose resin, starch-based resin, and composition thereof.

In according to a particularly preferred binder composition of the present invention, the dry strength tackiness agent comprises polyvinyl alcohol.The polyvinyl alcohol component can be any water-soluble or water dispersible, requires its molecular weight to be enough to form binder film.Usually, weight-average molecular weight is preferably in about scope of 40,000 to 120,000, more preferably in 70,000 to 90,000 scope.Solid polyethylene alcohol can be buied under several trade(brand)names, Evanol (Du Pont) for example, GELVATOL ^(Monsanto), VINOL ^(Air Products) and POVAL ^(KURARAY).The degree of hydrolysis of these grade products is in the scope of 80%-100%.Those skilled in the art are appreciated that reducing degree of hydrolysis and molecular weight can improve water-soluble but will reduce bounding force.Therefore, for specific end use, the character of polyvinyl alcohol must be optimized.Particularly preferred polyvinyl alcohol is the Evanol 71-30 by E.I.Du Pont Company (Wilmington) supply.The molecular weight of Evanol 71-30 is about 77,000, degree of hydrolysis about 99%.

In addition, the dry strength tackiness agent can comprise a kind of starch.Usually, be applicable to that implementing starch of the present invention is characterised in that to have water-soluble or form the ability of hydrophilic stabilising dispersions.Typical starch comprises W-Gum and potato starch, but this and do not mean that the scope of restriction suitable starches material.The preferably industrial waxy corn starch that is called Amioca starch (amylopectin).The difference of Amioca starch and conventional corn starch is that it is the starch of complete collateralization, and conventional corn starch contains amylose starch and amylopectin simultaneously.The various exclusive feature of amioca starch is in " Amioca-comes from the starch of wax shape corn ", H.H.Schopmeyer, and " foodstuffs industry ", further describes in the 106-108 page or leaf (the scrolling sign indicating number is 1476-1478) in December, 1945.Starch can be particulate form or dispersed.A kind of preferred starch (RediBOND) is a kind of standby dispersed substance.Granular starch, as the preferred fully boiling of Amylose1100 so that grain expansion.More preferably, starch granules boiling before just disperseing starch granules expand into to a certain degree.The starch granules of this high level expansion should be called " abundant boiling ".The dispersive condition is usually according to the quantity of the amylose starch of size, particulate degree of crystallinity and the existence of starch granules and different.Fully prepared in the about 30-40 of water slurry minute of the amioca starch of boiling can be by heating denseness about 4% in 190 ° of Fahrenheits (approximately 88 ° Celsius) starch granules.Other typical starch material that can be used can be from NationalStarch and Chemical Company (Bridgewater, NJ) obtain, comprise: the positively charged ion of modification or anionic starch, as having by modification as amino and be connected to those nitrogenous bases of methylol on the nitrogen and so on.The starch of considering this modification is more expensive than unmodified starch, the usually preferred latter.

The wet strengthening resin material

Binder composition of the present invention also can comprise about 0.05-5.0%, and the wet strengthening resin material of preferably about 0.1-2.5% weight is selected from as basal component: polymeric amide-epichlorohydrin resins, glyoxalated polyacrylamide resin, styrene-butadiene latex; Insoluble polyvinyl alcohol; Urea-formaldehyde resins; Polymine; Chitosan polymkeric substance and composition thereof.Wet strengthening resin is preferably and is selected from polymeric amide-epichlorohydrin resins, glyoxalated polyacrylamide resin, the water-soluble cationic resin of polyethylene imine resin and composition thereof.

Have been found that polymeric amide-epichlorohydrin resins is the useful especially positively charged ion wet strengthening resin of a class.Polymeric amide-epichlorohydrin resins preferably comprises Epicholorohydrin and has the water-soluble polymers reaction product of the water soluble polyamide of secondary amino group.The ratio of the secondary amino group of Epicholorohydrin and described polymeric amide preferably about 0.5: 1-2: 1.Water soluble polyamide is preferably derived from polyalkylene polyamine and the reaction that comprises the radical of saturated aliphatic di-carboxylic acid of about 3-10 carbon atom.The molar ratio of polyalkylene and di-carboxylic acid is preferably about 0.8: 1-1.5: 1.The radical of saturated aliphatic di-carboxylic acid is hexanodioic acid preferably, and the preferred diethylenetriamine of polyalkylene polyamine.Water soluble polyamide most preferably comprises the recurring group with following structural formula:

Wherein n and x are respectively 2 or higher, and R is the bivalent hydrocarbon radical that contains the di-carboxylic acid of 3-10 carbon atom.This resinoid can trade mark KYMENE ^(Hercules, Inc.) and CASCAMID ^(Borden) bought.This resinoid essential characteristic is that it is compatible with polyvinyl alcohol, that is, they are not separated in the presence of moisture polyvinyl alcohol each other.

Suitable such resin has description at USP 3,700 among 623 (authorizing Keim on October 24th, 1972) and the USP 3,772,076 (authorizing Keim on November 13rd, 1973), and these two pieces of patents are incorporated herein as a reference.One of this useful polymeric amide-epichlorohydrin resins commercial source is Hercules, and (Wilmington, Delaware), the said firm is with Kymene for Inc. ^557H, Kymene ^557LX and Kymene ^The 557ULX trade mark is sold this resinoid, wherein preferably uses Kymene ^LX.

Alkali-activatory polymeric amide-epichlorohydrin resins useful among the present invention is at Hercules, and (Wilmington Delaware) also has sale to Inc., and its trade mark is Kymeme ^TM450.The example of other commercial source of alkali-activatory polymeric amide-epichlorohydrin resins is that (St.Louis Missouri) sells with trade mark Santo Res Monsanto Company, and for example Santo Res 31.The material of these kinds is usually at USP 3,855,158 (1974 years, authorized Petrovich on December 17), USP3,899,388 (authorizing Petrovich on August 12nd, 1975), USP 4,129,528 (authorizing Petrovich on December 12nd, 1978), USP 4,147,586 (authorizing Petrovich on April 3rd, 1979), USP4,222, in 921 (the authorizing Van Eenam on September 16th, 1980) description is arranged all, all these patents all are introduced into this paper as a reference.

Find that also glyoxalated polyacrylamide resin can be used as wet strengthening resin.These resins all have description at USP 3,556 among 932 (authorizing Coscia etc. on January 19th, 1971) and the USP 3,556,933 (1971.1.19 authorizes Williams etc.), and these two pieces of patents are introduced into this paper as a reference.One of commercial source of polyacrylamide resin is that (Stanford, Connecticut), the said firm is with trade mark Parez for Cytec ^TM631NC sells a kind of this resinoid.

Find also that in the present invention operable other water miscible resin cation (R.C.) is urea-formaldehyde resins and terpolycyantoamino-formaldehyde resin.More common functional group is a nitrogen-containing group in these multifunctional resins, as amino and the methylol that is connected on the nitrogen.The polyethyleneimine: amine resins also can be used for the present invention.

Pigment

As described in above background parts of the present invention, need point out to the user, when bonded laminates is wetting, keep desired properties as wet laminated intensity and so on.In addition, as mentioned above and aforesaid U.S. Patent application 08/749708 described, the binder composition that lamination comprises pigment can produce sort signal, incorporates it into the present invention as a reference at this.

People know, and refractive index is to determine a principal element of the opaque effectiveness of pigment.The refractive index that following table 1 will be usually used in the pigment in the paper industry compares.

Table 1

Compound	Refractive index
		The titanium dioxide rutile-type	2.72
Detitanium-ore-type	2.55
		Zinc oxide	2.02
The kaolin filler	1.57
		Calcinated type	1.57
Lime carbonate is natural to grind	1.56
		The PCC-calcite	1.66
Talcum	1.57

Precipitated silica

1.45

Make pigment of the present invention in order to be suitable for, the refractive index of these inorganic coloring materials should be greater than about 1.4.This refractive index is preferably greater than about 1.7.The refractive index of particularly preferred inorganic coloring material is greater than about 2.0.

Except refractive index, the particle diameter of opacifying agent also produces main influence to the opacity of binder composition of the present invention.That is to say,, comprise opaquer than the composition of small particle size pigment for the pigment of given concentration in the binder composition.Be applicable to that pigment of the present invention has less than the particle diameter of about 1.4 microns intermediate value without sonication.This median particle diameter preferably less than about 0.8 micron, be more preferably less than about 0.6 micron.Below will provide the method for intermediate value of measuring in Test Methods section without the particle diameter of sonication.

Particularly preferred coloured material is titanium dioxide (TiO ₂).The TiO that has two kinds of crystal forms ₂: anatase octahedrite and rutile.Rutile-type is because its refractive index is higher and least transparent.In field of papermaking, knownly to reach given opacity, used rutile lacks about 15-20% than anatase octahedrite usually.Titanium dioxide is sold with dry powder form or as the slurries in water usually.For the present invention, the water slurry form is preferred, because mix easily with other component of binder composition of the present invention, and granules of pigments disperses more fully so that better opacity to be provided.

In order to make TiO ₂Keep suspending, can be at commercially available TiO ₂Add other component in the slurries.Especially, can use dispersing auxiliary to guarantee suspension TiO ₂Particle can not flocculate and sedimentation.Dispersing auxiliary has two kinds: stearic stablizer and electrostatic stabilization agent.Stearic stablizer is the TiO that surrounds suspension with the one layer of polymeric adsorption layer ₂Particle.Tristearin on the variable grain between the polymer layer interact can prevent particle fully near and assemble.Usually, stearic stable slurries are because polymkeric substance adsorption layer and unusual thickness.Titanium dioxide granule can also electrostatic means be stablized, and promptly adopts charge species to surround these particles.These materials can be cationic or anionic.Because most of TiO ₂Be used for paint and paper industry, and these industry all need be used the negatively charged ion slurries in its technology, so positively charged ion TiO ₂Slurries are uncommon.The example of suitable negatively charged ion electrostatic suspension auxiliary agent is a sodium polyacrylate, and United States Patent (USP) 4503172 (the name mandate of March 5 with people such as Farrar in 1985) is described this.This material can be by Allied Colloids of Suffolk, and VA obtains with Dispex N40X.

Suitable commercially available TiO ₂Slurries are Ti-Pure  RPS Vantage Rutile Paper Slurry, derive from Wilmington, the Dupont Company of DE.This material is a rutile TiO ₂A kind of negatively charged ion stable slurry in water, wherein nominal TiO ₂Solids content is 71.5%.The intermediate value of this material without the particle diameter of sonication (unsonicated) usually less than 0.5 micron.

Have been found that this TiO ₂Slurries are using TiO according to the present invention ₂Produce the visual signalling of required wet use properties during pigment.The applicant has been found that according to colored adhesive composition of the present invention should comprise TiO at least about 7% ₂Solid matter is to produce the visual signalling of gratifying required wet performance.TiO greater than 30% ₂Solids content can further not improve strength of signal.TiO ₂Solids content preferably should about 10-30%.TiO ₂Solids content is 15-25% more preferably from about.Those skilled in the art should be appreciated that, if use other pigment, so just need to adjust amount of pigment to produce gratifying visual signalling.As mentioned above, TiO ₂And the relative refractive index between alternative pigment can represent tentatively that the adjustment of needs has much.

Binder composition of the present invention, wherein said pigment is selected from kaolin, lime carbonate, zinc oxide and titanium dioxide.

In addition, organic colorant is as from Rohm﹠amp; Haas Corp., Philadelphia, the RopaqueHP91 of PA can be used for substituting to small part titanium dioxide.This organic colorant is the hollow polymer ball as the water miscible liquid supply.Because these balls are hollow, light just repeatedly bending the time by this dispersing of pigments body.Relative TiO ₂, the repeatedly crooked apparent refractive index that is produced can produce opacifying power.Because these organic colorants also are that negatively charged ion is stable, therefore, as mentioned above, can influence the stability and the opacity of the binder composition that comprises organic colorant equally with the uncompatibility problem of cationic wet strength resins.

Can in binder composition of the present invention, be used for substituting to the another kind of inorganic colourant of small part titanium dioxide be silica (as, fumed silica, colloided silica and analogue).Suitable fumed silica (fumedsilica) is AEROSIL 300 , derives from Degussa Corp.of Ridgefield Park, NJ.Can be clear that from embodiment 5 the colored adhesive composition that comprises this alternative inorganic colourant can produce aforesaid required turbidity and viscosity.The applicant also believes, uses silica to substitute part titanium dioxide and can reduce that tackiness agent is mixed and the abrasion of application device, because the basic particle diameter of silica granule is little.For example, the basic particle diameter of above-mentioned AEROSIL 300  is 7 nanometers, and above-mentioned TiO ₂Pigment then is 0.5 micron.

Optional cationic additive

People know, cationic substance portability positive charge, and anionic species then carries negative charge.A kind of the measuring of these electric charges is electric density.Below provide the method that is used to measure electric density in Test Methods section.The applicant has been found that according to proper adhesive composition of the present invention should have positive charge.That is, according to proper adhesive composition of the present invention be (positive charge density) of weak cation at least.The applicant believes, an advantage of the inventive method is, before beginning to add other component just in said composition the energy supply of one of negatively charged ion or cationic components can prevent a kind of like this situation, when wherein in adding said composition, remaining charged component, the partial confounding compound has had negative charge density and (has had been found that, when under low-energy condition, mixing each component, the loss that this negative charge density can increase cohesion, separates and cause opacifying agent to render a service).By enough energy are provided, can obviously reduce the formation of the cohesion of most of mixture with negative charge density and gained in mixing step.

Table 2 has been listed the charge density value of the representative component that is applicable to binder composition of the present invention.

Table 2

Component Electric density (microequivalent/gram) ^*

Cationic substance

Kymene557LX +3243

RediBond5320 +264

Anionic species

T1O ₂Slurries (Ti-Pure  RPS)-48

^*100% solid matter is the basis

The relative quantity of these components in composition determined the electric density of said composition.For example, have been found that the about 23%TiO that comprises about 1.5%Kymene 557LX and prepare according to the inventive method ₂Composition have the electric density of pact+185 microequivalent/grams.On the other hand, have been found that and comprise about 0.3%Kymene 557LX and about 23%TiO ₂Composition have the approximately electric density of-1.7 microequivalent/grams.Electric density in the finished product colored adhesive composition is preferably at least about+25 microequivalents/gram dispersible solid material.This electric density is preferably at least about+30 microequivalent/grams, more preferably at least about+50 microequivalent/grams.

Below will discuss, the inventive method can reduce the cohesion of pigment in the colored adhesive composition of preparation thus especially effectively.But still need in the finished product binder composition, keep minimum positive charge density, can make said composition the most stable like this.For example, a kind of special binder composition can not contain the enough cationic wet strength resins that keep positive charge density, and this positive charge density has increased cohesion and accumulative possibility.If the cationic substance in the said composition does not produce enough electric density,, can in said composition, add material (that is cationic additive) with positive charge density in order to compensate this insufficient positive charge density.Suitable material comprises: cationic starch (as, Celquat L200 derives from National starch and Chemical Co.of Bridgewater, NJ) and quaternary ammonium compound (as, derive from Witco Chemical Co.of Dublin, the DP-SC-505-91 of OH).Particularly preferred cationic additive is the polyamine with lower molecular weight of higher charge density.Particularly preferred this material is the electric density Cypro  515 of+6400 microequivalent/grams (100% solid matter is base) approximately, derives from Cytec of Stamford, CT.For example, if adding TiO ₂0.6% Cypro  515 is added in 0.3% the Kymene  557LX solution before, adding TiO so ₂The electric density of said composition is+35 microequivalent/grams afterwards, rather than above-mentioned-1.7 microequivalent/grams.Have been found that this electric density can produce sufficiently stable suspension to be used as laminating adhesive.

The production of tackiness agent

As mentioned above, preferred wet-strength resins Kymene  is the height cationic, therefore Kymene  and negatively charged ion is being stablized TiO ₂When slurries are used in combination, it can with binder composition, react as the anionic group in the negatively charged ion stable pigment dispersions, cause binder composition because of the cohesion layering with separate.1 pair of this phenomenon of following examples describes.

The applicant shockingly finds, by suitable mixing said ingredients, can overcome when producing stable composition cationic substance and anionic species bonded are known a difficult problem.

Specifically, the applicant has been found that by using the method for following detailed description, and wherein one of negatively charged ion or cationic components energy supply in said composition before adding other component can obtain obviously stable colored adhesive composition.If when " power supply device " can provide at least about 5 watts/kilogram when mixing liquid, this liquid was just by " energy supply ".Power supply device preferably should be able to transmit at least about 15 watts/kilogram when mixing liquid.This power supply device more preferably should be able to transmit at least about 25 watts/kilogram when mixing liquid.Test Methods section will provide a kind of method of definite energy (wattage/kilogram) that is transmitted.

Suitable power supply device comprises: can produce the batch mixer of high agitator tip speed, for example, derive from Sunbeam Corp.of Delray Beach, the mixing tank of FL (commodity are called Osterizer); The rotor/stator high-shear mixer, as derive from Charles Ross﹠amp; Son, Hauppauge, NY; With the on-line mixing device, as derive from Quadro Inc., Millburn, NJ, model is Quadro ZC.Particularly preferred power supply device is Breddo Likwifier, the LOR type, and by Breddo Likwifier of Kansas City, the MO supply.

In addition, the applicant finds that when these methods of use, the median particle diameter of pigment can be compared without the particle diameter of sonication with the intermediate value of pigment in the former pigment dispersion in the finished product binder composition.That is, the inventive method adopts these pigment dispersions in a kind of very effective mode, can obtain having the binder composition of high opacity like this.

Table 3 has most clearly provided this effectiveness, has wherein compared turbidity according to the colored adhesive composition of following examples 1 and the preparation of 2 described methods (turbidity is that a kind of tolerance-Test Methods section to opacity provides a kind of method of measuring turbidity).

Table 3

	Turbidity (NTU)	Intermediate value is without the particle diameter (micron) of sonication
			Composition according to the preparation of embodiment 1 method	1217 *	Bimodal (2.2,17.1)
Composition according to the preparation of embodiment 2 methods	3467 *	0.5

^*In 1000 ml waters, measure under the concentration of 0.5 gram tackiness agent.

Can clearly be seen that the binder composition for preparing according to embodiment 2 methods (the inventive method) has binder composition higher turbidity (bigger opacity) and the lower median particle diameter of obvious ratio according to embodiment 1 method (low energy mixing) preparation.

Under the situation of bound by theory not, the applicant believes, have in adding that a kind of charged component energy supply in composition can keep granules of pigments enough to separate before the component of opposite charges, like this gathering of granules of pigments is minimized (and can not increase average pigment particle size).The applicant has been found that if prepare the colored adhesive composition according to the present invention, so the granules of pigments in these compositions on average without the particle diameter of sonication just be no more than pigment in the pigment dispersion on average without about 2.5 times of the particle diameter of sonication.Usually, in the colored adhesive composition pigment on average without the particle diameter of sonication less than pigment in the pigment dispersion on average without about 1.5 times of the particle diameter of sonication.The applicant also believes, provides enough mechanical energy can reduce interaction between anionic species and the cationic substance when just second component being added first component.That is, making the composition viscosity that condenses and cause thus significantly increase (that is, layering and gelling) minimizes.

Although the first component energy supply to binder composition means the gathering that can reduce cohesion and granules of pigments before adding any other component as mentioned above, order of addition(of ingredients) also can influence the performance of finished product binder composition.Below use description to prepare a kind of particularly preferred method of binder composition of the present invention.

The first step of this preferred method provides the suitable cationic wet strength resins of aequum.For example, in order to prepare 100 parts of preferred adhesive compositions of the present invention, can provide the polymeric amide-epichlorohydrin resins of about 0.05-5 part.This resin is preferably in the solution that comprises about 10-15% weight resin solid matter.Particularly preferred method provides the polymeric amide-epichlorohydrin resins solution of about 12 parts 12.5% weight.Alternatively, can not keep suitable electric density (referring to above discussion), can before the cationic wet strength resins energy supply, provide a kind of above-mentioned place of cation material so if the desired concn of cationic wet strength resins is too low.

Then by above-mentioned to the appropriate device that mechanical energy wherein is provided, to this polymeric amide-epichlorohydrin resins solution energy supply.Importantly, this energy supply step will provide enough energy to cause the resin solution turbulization.For example, resin solution does not answer viscosity too high, otherwise most of mechanical energy that is provided can change into heat, causes solution temperature obviously to rise.Specifically, if measure according to the described method of following Test Methods section, the viscosity of resin solution should be less than about 500 centipoises.More preferably, this viscosity should be less than about 300 centipoises.

As mentioned above, suitable power supply device can provide energy at least about 5 watts/kilogram to resin solution by the first step.Being particularly preferred for power supply device of the present invention is Breddo Likwifier, the LOR type.

After the cationic wet strength resins energy supply, to wherein adding pigment dispersion.In order to obtain 100 parts above-mentioned preferred colored adhesive composition, at the pigment dispersion that in the solution energy supply, adds about 7-30 part continuously.For above-mentioned particularly preferred TiO ₂Dispersion adds 71.5% about 32 a parts weight fraction prose style free from parallelism.

Pigment dispersion preferably adds with a kind of like this speed, comprises positively charged ion wet tenacity solution or the dispersion of pigment in cationic wet strength resins solution to guarantee the body material in the mixing zone.In addition, can be of separation and the minimizing cohesion of insufficient energy to keep granules of pigments.Term used herein " mixing zone " is that the geometry by selected specific power supply device is determined, is meant the volume when energy is transferred to the liquid that needs energy supply or dispersion by power supply device.The applicant finds that a kind of is transmission number (Delivery Number) to the useful metrics that adds speed." transmission number " used herein is the non-dimensional number of the speed of rotation of a kind of adding speed that depends on pigment dispersion, agitator how much and agitator, can calculate according to following formula:

$Q=\frac{\left(\frac{\mathrm{PigWt}}{\mathrm{AddnTime}}\right)}{{\mathrm{nd}}^3\mathrm{\ρ}}$

$n=\frac{\mathrm{RotVel}}{60}$

Wherein:

Q=transmits number

The weight (kilogram) of pigment dispersion that PigWt=adds

AddnTime=adds the required time (second) of pigment

Density (the gram per centimeter of r=pigment dispersion ³)

The speed of rotation of RotVel=agitator (rpm)

The diameter of d=agitator (centimetre)

For example, when a collection of colored adhesive composition of the present invention of preparation, adopt following data:

The PigWt=36.97 kilogram;

AddnTime=240 second

R=2.2 grams per milliliter (TiO ₂Slurries comprise about 72%TiO ₂Solid matter)

RotVel＝1800rpm

D=24.3 centimetre

Gained transmission number is 1.63 * 10 ^-4From embodiment 3 as can be seen, this transmission numerical table shows, pigment dispersion is enough added in the mixing zone in case assemble (that is, intermediate value is starkly lower than 1 micron without the particle diameter of sonication) slowly.

In this preferred method, last required step is to add dry strength binder solution (still continuously to the liquid energy supply).The dry strength binder solution preferably adds after other component, because therefore the common viscosity height of these solution is difficult under acceptable intensification condition to these solution energy supplies.As mentioned above, the polyvinyl alcohol in starch-containing basic resin of dry strength binder solution preferred package or the water.The preferably about 2-14% of the concentration of the dry strength tackiness agent in this aqueous solution, and in preparation during 100 parts of finished product binder compositions adds the adhesive solids material of about 2-7 part in this binder composition.

Alternatively, other component is added after mixing above-mentioned each material.For example,, can keep a part of dilution water, the difference between can compensating like this batch on each raw material in order to control final viscosity and solids content.

Other tackiness agent production method

Order of addition(of ingredients)

Although aforesaid method is owing to can make the granules of pigments maximum dispersion and reduce particle aggregation and preferred, other method, especially other order of addition(of ingredients) are also within the scope of the invention.For example, the applicant can consider a kind of like this order of addition(of ingredients), comprising following steps: 1) provide a kind of dry strength binder solution; 2) to this dry strength binder solution energy supply; 3) provide a kind of negatively charged ion stable pigment dispersions; 4) pigment dispersion is sneaked in the dry strength binder solution to form a kind of colored adhesive mixture; 5) provide a kind of cationic wet strength resins solution; Then 6) wet-strength resins solution is sneaked in the colored adhesive mixture.Compare with the low energy blending means,, assemble and reduce and stablize according to the obvious opacity raising of the colored adhesive composition of this alternative method preparation.Specifically, comprise above-mentioned preferred TiO ₂The intermediate value of the binder composition of pigment is about 1 micron without the particle diameter of sonication, and initial disengaging time was greater than 24 hours.If result shown in these results and the previous table 2 is compared, the low energy blending means of so relative embodiment 1, this improvement is significant.

Power supply device

Be applicable to other power supply device of the present invention be a kind of can be by in liquid medium, forming ultrasonic vibration to the mixing tank of its energy supply (a kind of suitable device by Sonic Corp.of Stratford, the sonolator that CT produces).Sonolator is a kind of online system, and it has the type hole with high linear speed pumping liquid, liquid mixture or the solid dispersion in liquid by one, can produce ultrasonic vibration like this.The blade of liquid stream bump cantilever in liquid stream.The liquid stream that flows through blade produces vibration in blade, produce cavatition so that the energy of flow is changed into mixing/dispersion energy then in liquid stream.

Lamination flower and lamination

After cambial paper-making process finishes, one or more layers can be carried out embossing and lamination.If use colored adhesive composition of the present invention to carry out embossing/lamination step, embossing/lamination is exactly that the method for patterning that provides vision to show to desired properties is provided a kind of can the generation so.

Can carry out embossing in accordance with the following methods: joint is described among this USP 3,414,459 at common transfer (authorizing Wells December 3 nineteen sixty-eight) joint (knob-to-knob) embossing; Nested embossed method (nested embossing process), this authorizes the USP3 of Nystrand on January 19th, 1971, be described in 556,907; Or double layered pressed method (dual ply process), this is described in 294,475 (the authorizing McNeil on March 15th, 1994) at the USP5 of common transfer, and all these patents are incorporated herein as a reference.

Concerning the present invention describe and claimed embodiment, these embossing can be opened with the intervals of 0.05-0.07 inch, and the far-end area of 0.001-0.100 square inch is arranged.Each embossing can be made on the knotty roller being permitted, and these joints are from the outstanding 0-0.120 inch in roller surface.These embossing can be circular, goose is avette or irregularly shaped.

Each embossing all has far-end, and binder composition of the present invention is administered at least a portion of far-end, forms according to laminated thin page or leaf goods of the present invention.The adhesive solids material preferably is administered on some far-end at least on the thin page or leaf of one deck at least with ironed page of goods of form layers with the speed of about 12-20 pound adhesive solids material/ton paper (6-10 gram adhesive solids material/kilogram paper).More preferably use about 14-18 pound adhesive solids material/ton paper (7-9 gram/kilogram).Term used herein " adhesive solids material " is meant the nonaqueous component in the binder composition of the present invention, comprising wet-strength resins, dry strength additive, TiO ₂, and any dispersing auxiliary maybe can add other material in this binder composition.

Embodiment 4 has described a kind of embossing or lamination of being particularly preferred for to produce the method according to laminated thin page or leaf goods of the present invention.

The applicant believes that following indefiniteness embodiment is used to illustrate the present invention.

Embodiment

Embodiment 1

This embodiment is used to illustrate the performance by the cohesion mixture of cationic wet strength resins and negatively charged ion stable pigment dispersions and dry strength binder solution of using conventional blending means preparation.

Prepare the colored adhesive composition in accordance with the following methods: 1) about 13 parts of cationic wet strength resins solution are provided, and wherein comprising about 12.5%Kymene  557LX resin and pH value is about 3.0; 2) use derives from Lightnin of Rochester, and the Lightnin TS2010 type mixing tank (this mixing tank can provide about 1.7 watts/kilogram energy to solution) of NY begins to stir wet-strength resins solution; 3) under continuously stirring, add 72% solids content TiO of about 23 parts pH value about 8.4 ₂Dispersion (from the Ti-Pure  RPS Vantage rutile pulping liquor of DuPont); 4) under continuously stirring, add dry strength additive (from the ELVANOL 71-30 of the DuPont) solution of about 64 parts resin solid content about 7.4%; Then 5) under continuously stirring, add entry to 100 part as required.

Table 4 has been listed the resulting performance data of this binder composition of assessment.

Table 4

Performance Value

PH value 4.3

Intermediate value is without the particle diameter (μ m) of sonication

First peak 17.1

Second peak 2.2

Turbidity ^*1217

Initial disengaging time 4 hours

^*Under the concentration of 0.5 gram tackiness agent in 1000 ml waters, measure.

Embodiment 2

This embodiment has adopted material, concentration and the order of addition(of ingredients) identical with embodiment 1, but adopts the inventive method, has obtained being suitable for connecting the painted laminating adhesive composition of two-layer or multi-layered tissue paper.Specifically, used can to about 110 watts/kilogram laboratory blender of liquid energy supply (as, derive from the Osterizer of Sunbeam Corp.of Delray Beach FL).

Table 5 has been listed the resulting performance data of this binder composition of assessment.

Table 5

Performance Value

PH value 4.3

Intermediate value is without the particle diameter (μ m) 0.5 of sonication

Turbidity ^*3467

Initial disengaging time＞4 weeks

Embodiment 3

This embodiment is used for explanation and uses the technical scale mixing device to prepare according to colored adhesive composition of the present invention.

Device:

Mixing tank Breddo Likwifier, the LOR type, 50 gallons of sizes, the 30Hp motor, adjustable speed (640-2300rpm) derives from Breddo Likwifier of Kansa City, MO

Impeller 1) standard plate-parts number 8-711-0004

2) fluted disc-parts number 8-711-0691 is arranged

Form

Component %

Cationic wet strength resins solution 12

TiO ₂Dispersion 32

Dry strength additive solution 55

Water 1

Amount to 100

Table 6 has been listed the performance according to several colored adhesive batch composition of various processing condition preparations.

Every batch of several particle diameter turbidity that add the energy intermediate value without sonication of big or small speed transmission of table 6 test dialer

Type (kilogram) is (NTU) 1 standard 116 1,800 1.62 10 of (watt/kilogram) (rice) (rpm) ^-435.2 0.679 3,567 2 has tooth 116 1,800 1.62 10 ^-490.3 0.566 3,721 3 has tooth 230 1,800 5.15 10 ^-488.1 0.577 does not obtain

Embodiment 4

This embodiment discusses the various performances of use according to the colored adhesive composition lamination laminated paper product of embodiment 2 methods preparation.These paper products can be made by the cellulosic fibre of the two-layer Bounty of being usually used in board paper handkerchief, and these paper handkerchiefs are by Procter ﹠amp; Gamble Company of Cincinnati, OH (transferee of the present invention) supply.Make by 65% northern softwood kraft pulp, 35%CTMP for every layer, and it quantitatively is 14 pounds/3000 foot 2.Every layer is come embossing by oval projections in nested embossed technology, these projections have 0.084 inch main shaft at far-end, 0.042 inch countershaft and projection is high 0.070 inch.These projections in the concentric diamond pattern of 45 degree pitches at a distance of about 0.118 inch.Prepare two complementation layers, cooperate on the nip in the zero stand-off then to couple together, thereby make every layer of monoblock type laminate with about 33 projection/in2s.

Embodiment 3 methods provide a kind of binder composition that comprises 5.75% total binder solid matter (wherein 1.5% is Kymene , the 4.25%th, polyvinyl alcohol).This binder composition also comprises 23% titanium dioxide solid matter.This binder composition is administered on every layer the projection.Solid matters all in the binder composition all is administered on the paper product.The wet laminated intensity of gained paper product is 5.5 gram/inches, and doing laminated intensity is 10.4 gram/inches.Below in Test Methods section the method be used to measuring wet laminated intensity and do laminated intensity is described.

In table 7, the tissue products that will press with the adhesive composition layer of the present invention preparation and other commercially available paper handkerchief wet laminated intensity and dried laminated strength ratio.

Table 7

Sample Manufacturers Wet laminated intensity Do laminated intensity

(gram/inch) (gram/inch)

The assignee of the present invention 5.5 10.4

BOUNTY transferee 3.9 10.1

BRAWNY ^* James River 3.1 10.1

SPARKLE ^* Georgia Pacific 3.0 7.0

MARDIS GRAS ^* Ft.Howard 3.4 7.6

VIVA-2-PLY ^* Scott 3.0 4.4

HI-DRI ^* Kimberly Clark 3.4 5.5

^*Data are from U.S. Patent application 08/835039.

Every kind of wet and dried laminated intensity in the table 6 is all represented the mean value of at least 5 samples.Certainly, for dried laminated strength trial, each in 5 samples all represented the mean value of 4 test samples.Can be clear that from the data of table 7 binder composition of the present invention provides the improved basically laminated intensity that wets when keeping the dried laminated intensity that can match in excellence or beauty with commercially available paper handkerchief.If will use the laminated paper handkerchief of adhesive composition of the present invention to be immersed in the water, the pattern of colored adhesive is just high-visible so.If similarly the listed commercially available paper handkerchief of table 7 is flooded, does not then have apparent pattern.

Embodiment 5

This embodiment is used to illustrate the prescription of the painted laminating adhesive of the present invention that comprises equivalent material.Table 8 has been listed the composition according to laminating adhesive of the present invention, wherein comprises simultaneously to substitute inorganic colourant and optional cationic additive.

Table 8

Component Concentration

( Weight percentage)

Dry strength additive ¹4.5

Pigment ²18.0

Cationic wet strength resins ³0.3

Optional cationic additive ⁴0.7

Substitute pigment ⁵1.0

Water capacity to 100%

1.ELVANOL71-30

2. the solid matter that produces by Ti-Pure  RPS Vantage rutile paper pulp

3.Kymene557LX

4.Cypro515

5.Aerosil300

Basically prepare composition according to the preferred method of the present invention, wherein when mixing each component, use laboratory blender (Osterizer) to the composition energy supply.The final product composition having assessment is as follows: 1) do not have the visible centrifugation after 14 days; 2) turbidity-2600NTU that can match in excellence or beauty with other composition of the present invention; 3) if use gauge stick (to derive from PaulN.Gardner Co. on composition being administered to thin page or leaf ground the time, Inc.of Pompano Beach, FL, model is size 8) with control coating thickness, the whiteness of the thin layer of present embodiment binder composition just can compare favourably with the whiteness of using the binder composition on the thin page or leaf of the row ground according to the employing same way as of embodiment 2 preparations so; With 4) viscosity can with other composition of the present invention-170 centipoises that compare favourably.

Testing method

Do laminated intensity

The sample of four paper products is provided.After the adhesive composition completely solidified, with aging at least 2 weeks of these samples.Downcut three inches bars along sample total length direction from the center of each sample.Wherein two are downcut along machine direction, and two is (that is, between the hole of machine direction or between the limit of cross machine) of downcutting along the direction of vertical machine in addition.These are separated slightly along any one edge of three cun, so each layer is independent with other layer.The gauge length that each layer hand come up to sample is 2 inches.

Each layer is placed in the intermediate plate (jaw) of drawing machine.Suitable tensile testing machine is Model 1451-24, by Thwing/Albert company (Philadelphia, Pennsylvania) supply.The Thead off-set die head velocity of separation is arranged on 20 inch per minute clocks, has moved 7.5 inches from 2.0 inches initial interval.Only write down Thead off-set die head and move last six inches data.All four samples all will be done tension test.These four data are provided a single laminated intensity level after average, and this value has promptly been represented the laminated intensity of the product that all four samples take from.

Must be noted that and make the isolating sample part of the machine of being stretched not contact the lower intermediate plate of drawing machine or lower Thead off-set die head.If such contact takes place, will on loadometer, show a unreasonable high reading.Equally also to note will be separated sample part and each layer isolating sample of machine that has been stretched partly do not contact.If such contact, apparent laminated intensity will irrationally raise.If any carrying above-mentioned touch, this data point will be rejected and test a new sample again.

Wet laminated intensity

The sample of four kinds of paper products is provided.After the adhesive composition completely solidified, with aging at least 2 weeks of sample.Downcut from the center of each sample three inches bars along sample total length direction (as, for the material that changes into commercially available paper handkerchief, between each hole).Wherein two are downcut along machine direction, and two is (that is, between the hole of machine direction or between the limit of cross machine) of downcutting along the direction of vertical machine in addition.These are separated slightly along any one edge of three cun, so each layer is independent with other layer.The gauge length that each layer hand come up to sample is 2 inches.

Each layer separated along 3 inches limits of sample.With not separated sample part, the part of promptly not putting into the drawing machine clip is immersed in distilled water.Behind the dipping, sample is taken out from water immediately, and make its 60 second of draining on a draining rack.Be furnished with nylon wire side sieve on the draining rack, the diameter that forms the nylon wire of sieve is 0.015 inch, 0.25 inch at interval.Drying rack is with 45 ° angle placement with respect to the horizontal plane.When dry sample on drying rack, the placement of sample should make that the long limit of sample is consistent with the gradient of drying rack downwards.Make sample smooth as much as possible on the drying rack thereby the limit that this layer separates is recovered to together, sample has suitably drained redundant moisture simultaneously.After making sample by this way, on drawing machine, test this sample with the method for the dried laminated intensity of above-mentioned test.

Viscosity

General introduction

This method is applicable to the viscosity of measurement as the shearing rate function.Sample is placed in the narrow annular volume between two concentric cylinders.Inner cylinder rotates with controlled annular speed, gained moment of torsion or be the measuring of viscosity that is placed on sample between the two by the power that sample produced between two right cylinders.

Device

Viscometer, a kind of suitable viscometer derive from Paar Physica USA.Inc.of Edison, NJ, model MCl.

The setting of device

1) sets viscometer according to the requirement of manufacturers.

2) temperature of sample and device should be 23 ± 1 ℃.

Method

1) uses sample to be assessed, exterior circular column is filled into scalar quantity.

2) exterior circular column is inserted in the viscometer, guarantee that inner cylinder is positioned at its center and the exterior circular column fix in position.After the exterior circular column fix in position, placed at least 10 seconds, sample is filled in two annular volume between the right cylinder, begin to scan viscosity then.

3) viscometer is set in 10-1000 second ^-1Between scan, use oblique ascension/oblique deascension program (ramp up/ramp down protocol) to carry out viscosity measurement then.Partly measure 50 times at oblique ascension, partly measure 50 times in oblique deascension.

The record of data and analysis

Write down each oblique deascension part in two samples, in 10-1000 second by program ^-1Viscosity under the shearing rate.

Electric density

General introduction

The electric density of dispersion or colloidal solution can be measured by the electromotive force of measuring between a pair of spaced electrode (streaming potential); a surface of one of them electrode and sampling receptacle is adjacent; in this sampling receptacle; the particle of dispersion or the macromole of colloidal solution are adsorbed, and another electrode then is arranged in the free volume of sampling receptacle.By an oscillating piston of setting electromotive force, the counter ion of all charged particles or macromolecular substance are flowed.Use standard polyelectrolyte then,, measure electric density (in microequivalent/gram) sample titration to 0 streaming potential (that is) to equi-potential with opposite charges.

Device

The particle charge detector: a kind of device of measuring electric density that is applicable to derives from Mutek Analytic as particle charge detector PCD 02, Inc.of Marietta, GA.

Titrator: suitable titrator is automatic end-point titrator DL2 1 type of Mettler with two piston burets, derives from MUTEK Analytic, Inc.of Marietta, GA.

Reference material

The standard polyelectrolyte solution also derives from MUETEK Analytic.The positively charged ion standard substance is the diallyl dimethyl ammoniumchloride of 0.001N.The negatively charged ion standard substance is the polyvinyl sulfuric acid sodium of 0.001N.

Operation

1), sets and proofreaies and correct the particle charge detector according to the requirement of manufacturers.Importantly, in order to measure accurately 15 ℃ of envrionment temperature should exceeds, preferred about 25 ℃.

2), set and proofread and correct titrator according to the requirement of manufacturers.

3) clean the sample pool and the piston of particle charge detector with sample.Can filtered sample (100 mesh filter screen) removing macrobead, otherwise can influence the operation of piston, although this is the sub-fraction charge species.

4) sample with controlled quatity is assigned in the sample pool of cleaning.May need to carry out preliminary titration need to determine the sample size of 0.5-15 milliliter titrating solution.At least need 10 milliliters of liquid to cover two electrodes.Sample can dilute with deionized water, needing to obtain at least 10 ml samples of 0.5-15 milliliter titrating solution.

5) piston is inserted in the sampling receptacle, then container is put into the particle charge detector, guarantee the electrode contact and make piston and the drives structure engagement.

6) open piston, make streaming potential stablize (about 2 minutes).

7) use suitable polyelectrolyte solution to come the titration sample to iso-electric point.That is, use anionic polyelectrolyte titration positively charged ion sample, use cationic polyelectrolyte titration negatively charged ion sample.

The record of data and analysis

1) writes down the sample titration to the required titration dosage of iso-electric point.

2) use following formula to calculate electric density (microequivalent/gram):

$q=\frac{V\×C\×1000}{W}$

Wherein: V is required volume of titrant (milliliter); C is Polyelectrolyte Concentration (microequivalent/milliliter); And W be in the sample solids content (as, for 0.1%TiO ₂10 ml samples of suspension, the W=0.01 gram)

3) report each measuring result of being done.

Size distribution

General introduction

Use light scattering device to measure the size distribution of the granules of pigments that forms in the methods of the invention.Can use relevant and incoherent light source, this depends on the desired extent of particle diameter.

Device

Suitable device derives from Horiba Instruments, Inc.of Irvine, CA, model LA910.Horiba LA910 can use the scattering system to measure size distribution (PSD).Can use coherent source (laser) and incoherent light source to measure the interior PSD of wide region.This device can be measured four distributions (volume, number, area and length) of given sample.Software is connected on the computer controlling this device, and the actual light intensity data that records is changed into any above-mentioned distribution.Preferred volume distributes should follow structural changes.Median particle diameter can suitably be described the situation that deviates from proper distribution like this as the monodrome descriptor of PSD and preferred.Horiba LA910 can adopt low energy sonication (about 40 watts) to separate aggregate.In order to understand possibility better, preferably need not to measure PSD under the sonication owing to any congregation that specific blend technology causes.

Reference material

Calibration standard thing: Nanosphere ^TMThe polystyrene standard particle, by Duke Scientific ofPalo Alto, CA provides.These standard substances can be followed the tracks of NIST.

The setting of device

Relative refractive index (RRI): 2.00-0.00i

Stir: 3

Circulation: 4

Sonication: close

Method

1), sets and proofreaies and correct this instrument according to the requirement of manufacturers.

2) the measurement symbol on the computer screen is clicked in water filling sample pond then, measures the baseline of blank (degassing, deionized water) size distribution with inspection apparatus.

3) 150 milliliters of degassings, deionized waters are put into sample pool, then this sample pool is inserted in the device.

4) dripping sample, is about 70-75% up to the printing opacity ratio that records by this device (blue ratio).

5) click measurement symbol on the computer screen to collect sample data, determine the size distribution of sample then.

The record of data and analysis

1) size distribution of at least two samples of measurement.

2) determine that this distribution is polydisperse or monodispersed.

3) for single discrete distribution, the record median particle diameter.

4) distribute the particle diameter that record is determined by each distribution of peaks for polydispersion.

Turbidity

General introduction

Turbidity is a kind of tolerance to liquid suspension opacity/haziness.Turbidity is measured by the amount of light scatter of determining suspended particle.

Instrument

Turbidometer: suitable turbidometer derives from HACH Company of Loveland, CO, model 2100AN.

Reference material

The standard turbidity material that turbidity value is lower than 0.1,20,200,1000,4000 and 7500 turbidity units (NTU) also derives from HACH Company.

Method

1), sets and proofreaies and correct turbidometer according to the requirement of manufacturers.

2) with 1000 ml waters dilution, 0.4 gram colored adhesive, mixed then 1 minute.Suitable magnetic stirring apparatus, as Corning PC-351 type derive from Corning Glass Works (Corning, NY).

3) with dilute sample balance 1 minute.

4) suitable volume (about 30 milliliters) is transferred in the sample pool.

5) measure turbidity according to the requirement of manufacturers.

6) the measured turbidity of record.

The record of data and analysis

1) with turbidity unit (NTU) record turbidity value.

Mixing energy

General introduction

Measure electric current and voltage, be used to calculate the power that is transferred on the power supply device then.

Instrument

Power analyzer: suitable power analyzer derives from Fluke Corp.of Everett, WA, and model is 41B Power Harmonics Analyzer.

The ampere probe: the 80I-1000s type also derives from Fluke Corp.

Method

1) guarantees to come the corrected power meter according to the requirement of manufacturers.

2) ampere probe is placed near one of three conductors of the supply lines that is used for power supply device.Voltage probe is connected on other two conductors of supply lines.Fluke 41B calculates the three phase power reading by the simple single-phase measurement to balance three conductor loadings.The software that use provides with instrument (FlukeView 3.0 editions) is with power measurement values transmission and record on the Microsoft Excel Spread Sheet.

3) less water is placed near the bottom seal power consumption when measuring slack tank.Measure the power consumption of specific power supply device in whole velocity range to be assessed.

4) in each addition step of above-mentioned tackiness agent production technique, per 10 seconds are by power analyzer recording power reading at least 5 times.If desired, data acquisition hardware and software can be used for sample, automatic then recording power reading.

The record of data and analysis

1) power consumption when reinforced deducts the power consumption under travelling speed, calculates the pure horsepower of each addition step thus.

2) pure horsepower is needed the quality of the material of energy supply after divided by addition step, calculate the pure horsepower of the unit mass of each step thus.

3) pure horsepower of the each recording step of record and the pure horsepower of unit mass.

Claims (10)

1. binder composition that is used for lamination absorptivity paper product, described binder composition comprises following material:

Water-soluble or the water-dispersible dry strength tackiness agent of about 2-7% weight;

The water-soluble cationic wet-strength resins of about 0.05-5% weight;

The water of about 58-91% weight;

It is characterized in that described binder composition also comprises the granules of pigments in the described binder composition of being suspended in of 7-30% weight; With

The negatively charged ion dispersing auxiliary that described granules of pigments is used, the intermediate value of wherein said granules of pigments are no more than 2.5 times of median particle diameter in described pigment dispersion without the particle diameter of sonication.

2. according to the binder composition of claim 1, wherein said dry strength adhesive material be selected from polyvinyl alcohol, polyvinyl acetate (PVA), carboxymethyl cellulose resin, starch-based resin, and composition thereof.

3. according to any one binder composition in the aforementioned claim, wherein said pigment is selected from kaolin, lime carbonate, zinc oxide and titanium dioxide.

4. according to any one binder composition in the aforementioned claim, wherein said pigment slurry offers described binder composition as the dispersion in water, and described dispersion contains described negatively charged ion dispersing auxiliary.

5. according to any one binder composition in the aforementioned claim, wherein said water-soluble cationic resin be selected from polymeric amide-epichlorohydrin resins, glyoxalated polyacrylamide resin, polyethylene imine resin, and composition thereof.

6. according to the binder composition of claim 5, wherein said polymeric amide-epichlorohydrin resins comprises Epicholorohydrin and the reaction product that contains the polymeric amide of secondary amino group, and the ratio of the secondary amino group of Epicholorohydrin and described polymeric amide is 0.5: 1-2: 1.

7. absorptivity paper product, described paper product comprises two layers of paper at least, and wherein said layer uses and carries out adhesive lamination according to laminating adhesive composition arbitrary in the aforementioned claim.

8. according to the absorptivity paper product of claim 7, wherein said paper product comprises 6-10 gram adhesive solids material/kilogram paper.

9. according to the absorptivity paper product of claim 7 or 8, wherein said paper product is a paper handkerchief.

10. colored adhesive method for compositions that is used for production claim 1, described method comprises following steps:

A) provide first resin aqueous solution or dispersion;

B) provide power supply device, it is characterized in that, described power supply device can provide at least 5 watts/kilograms power to described first resin solution or dispersion;

C) use described power supply device to described first resin solution or dispersion energy supply;

D) provide the water dispersion of granules of pigments, described granules of pigments has median size;

E) use described power supply device, described pigment dispersion is sneaked in described first resin solution or the dispersion;

F) provide second resin aqueous solution or dispersion; Then

G) use described power supply device, described second resin aqueous solution or dispersion are sneaked in the described mixture of described first resin solution and described pigment dispersion, form described colored adhesive composition, the intermediate value of wherein said granules of pigments in described colored adhesive composition is no more than the intermediate value of described granules of pigments in described pigment dispersion 2.5 times without the particle diameter of sonication without the particle diameter of sonication.