WO2021182566A1

WO2021182566A1 - Paper machine roll coating material and paper machine roll

Info

Publication number: WO2021182566A1
Application number: PCT/JP2021/009769
Authority: WO
Inventors: 宏哉島崎
Original assignee: ヤマウチ株式会社
Priority date: 2020-03-12
Filing date: 2021-03-11
Publication date: 2021-09-16

Abstract

This paper machine roll coating material contains a urethane prepolymer component which is a reaction product of an aliphatic polyol and diisocyanate, and a curing agent component containing a diamine-based curing agent and an aliphatic polycarbonate diol, and has a durometer A hardness of 65-99 on the surface. This paper machine roll includes a roll core material and the paper machine roll coating material with which the outer periphery of the roll core material is coated.

Description

Paper machine roll dressing and paper machine roll

The present invention relates to a roll coating material for a paper machine and a roll for a paper machine containing the same.

The international publication WO2016 / 043290 pamphlet (Patent Document 1) includes a core material and a coating material formed on the core material as an industrial roll used in the paper manufacturing industry, and the coating material is preferably a polyurethane resin. Disclosed are industrial rolls selected from the group consisting of epoxy resins, polyurea resins and synthetic rubbers.

Japanese Unexamined Patent Publication No. 56-028312 (Patent Document 2) discloses a polyurethane rubber roll in which a polyurethane rubber coating layer is provided on the outer periphery of a core material via a curable resin-impregnated fiber reinforcing layer (FRP layer).

Japanese Unexamined Patent Publication No. 57-118898 (Patent Document 3) discloses a press roll provided with a resin layer and a polyurethane rubber layer formed on the surface of the resin layer on the surface of the core material.

International Publication WO 2016/043290 Pamphlet Japanese Unexamined Patent Publication No. 56-028312 Japanese Unexamined Patent Publication No. 57-11898

However, an industrial roll comprising a polyurethane elastomer disclosed in International Publication WO2016 / 043290 (Patent Document 1) as a coating material, a polyurethane rubber roll disclosed in Japanese Patent Application Laid-Open No. 56-028312 (Patent Document 2), and Japanese Patent Application Laid-Open No. 56-028312 (Patent Document 2). The press roll disclosed in Japanese Patent Application Laid-Open No. 57-118898 (Patent Document 3) has excellent elastic performance when used as a roll for a paper machine, but is made of polyurethane due to the moist heat environment, chemicals, coating liquid, etc. at the time of paper making. There is a problem that the coating material formed of the elastomer deteriorates and unevenness, wear, etc. occur on the surface of the coating material of the roll, which adversely affects the papermaking.

Therefore, the present invention provides a roll coating material for a paper machine that does not adversely affect paper making by suppressing deterioration of the coating material formed of the polyurethane elastomer during paper making, and a roll for a paper machine containing the same. The purpose.

The roll coating material for a papermaking machine according to one aspect of the present invention contains a urethane prepolymer component which is a reaction product of an aliphatic polyol and a diisocyanate, and a curing agent component containing a diamine-based curing agent and an aliphatic polycarbonate diol. The Durometer A hardness on the surface is 65 or more and 99 or less.

The roll for a paper machine according to one aspect of the present invention includes a roll core material and a roll covering material for a paper machine according to the above aspect that covers the outer periphery of the roll core material.

According to the roll coating material for a paper machine and the roll for a paper machine, the roll coating material for a paper machine and the roll coating material for a paper machine that do not adversely affect the paper making by suppressing deterioration of the coating material formed of the polyurethane elastomer during paper making. A roll for a paper machine including the above can be provided.

It is the schematic which shows the roll for a paper machine which concerns on one aspect of this invention.

[Embodiment 1: Roll Covering Material for Paper Machine]
The roll coating material for a papermaking machine of the present embodiment contains a urethane prepolymer component which is a reaction product of an aliphatic polyol and a diisocyanate, and a curing agent component containing a diamine-based curing agent and an aliphatic polycarbonate diol, and is a durometer on the surface. A hardness is 65 or more and 99 or less. The roll coating material for a paper machine of the present embodiment can prevent the paper making from being adversely affected by suppressing the deterioration of the polyurethane elastomer constituting the coating material.

(Urethane prepolymer component)
The urethane prepolymer component constituting the roll coating material for a paper machine of the present embodiment is a component derived from the urethane prepolymer and is a reaction product of an aliphatic polyol and a diisocyanate. Here, the urethane prepolymer can form a polyurethane elastomer by reacting with a curing agent component described later, and contains an isocyanate group (NCO group) at at least one end of the urethane prepolymer.

The aliphatic polyol that reacts with diisocyanate to obtain a urethane prepolymer is not particularly limited, but is at least one of a polyether polyol and a polyester polyol from the viewpoint of forming a urethane elastomer whose deterioration is suppressed during papermaking. Is preferable. Preferred examples of the polyether polyol include polyethylene glycol (hereinafter, also referred to as PEG), polypropylene glycol (hereinafter, also referred to as PPG), polytetramethylene glycol (hereinafter, also referred to as PTMG) and the like. Preferable examples of the polyester polyol include polycaprolactone-based polyols, polycarbonate-based polyols, polyethylene adipate-based polyols, polybutylene adipate-based polyols, and polyhexene adipate-based polyols. These aliphatic polyols can be used alone or in combination of two or more, and modified products thereof can also be used.

The diisocyanate obtained by reacting with an aliphatic polyol to obtain a urethane prepolymer is not particularly limited, but is limited to toluene diisocyanate (hereinafter, also referred to as TDI), diphenylmethane diisocyanate (hereinafter, also referred to as MDI), and dicyclohexylmethane diisocyanate (hereinafter, H-MDI). , 1,4-phenylene diisocyanate (hereinafter, also referred to as PPDI), isophorone diisocyanate (hereinafter, also referred to as IPDI) and the like are preferably mentioned. These can be used alone or in admixture of two or more.

(Curing agent component)
The curing agent component constituting the roll coating material for the papermaking machine of the present embodiment is a component derived from a curing agent that reacts with the polyurethane prepolymer, and is also referred to as a diamine-based curing agent and an aliphatic polycarbonate diol (hereinafter, also referred to as an aliphatic PCD). )including. The roll coating material for a paper machine contains an aliphatic polycarbonate in addition to a diamine-based curing agent as a curing agent component, so that a urethane elastomer whose deterioration is suppressed during papermaking is formed.

The diamine-based curing agent is not particularly limited, but from the viewpoint of forming a urethane elastomer whose deterioration is suppressed during papermaking, 4,4'-methylene-bis (2-chloroaniline) (hereinafter, also referred to as MOCA). ), Trimethylene-bis (4-aminobenzoate) (hereinafter, also referred to as CUA-4), diethyltoluenediamine (hereinafter, also referred to as DETDA), dimethylthiotoluenediamine (hereinafter, also referred to as DMTDA), 4,4'- Methylene-bis (3-chloro-2,6-diethylaniline) (hereinafter, also referred to as M-CDEA) and the like are preferably mentioned. Further, from the above viewpoint, MOCA is more preferable as the diamine-based curing agent.

The aliphatic PCD is not particularly limited, but the number average molecular weight of the aliphatic PCD is preferably 500 or more and 2000 or less, and 500 or more and 1000 or less, from the viewpoint of forming a urethane elastomer whose deterioration is suppressed during papermaking. More preferably, it is more preferably 500 or more and 800 or less. Here, the number average molecular weight of the aliphatic PCD can be measured by gel permeation chromatography (hereinafter, also referred to as GPC). The aliphatic PCD is not particularly limited, but since it is liquid at room temperature (for example, 25 ° C.), it is easy to handle, so that it is an alkyl carbonate diol having 5 carbon atoms (hereinafter, also referred to as C5-CD) and a carbon number of carbon atoms. A copolymer of an alkyl carbonate diol (hereinafter, also referred to as C6-CD) having a value of 6 (hereinafter, also referred to as a C5 / C6 copolymer) is preferable.

The content of the aliphatic PCD in the roll coating material for the paper machine is not particularly limited, but 2.5 mass from the viewpoint that the roll coating material for the paper machine is composed of a urethane elastomer whose deterioration is suppressed during paper making. % Or more and 17.5% by mass or less are preferable, and 2.5% by mass or more and 16% by mass or less are more preferable. Here, the content of the aliphatic PCD is particularly preferably 5% by mass or more from the viewpoint of suppressing deterioration of the urethane elastomer constituting the roll coating material for the paper machine during paper making, and is on the surface of the roll coating material for the paper machine. From the viewpoint of suppressing a decrease in the durometer A hardness, 15% by mass or less is particularly preferable.

The mass ratio of the diamine-based curing agent to the aliphatic PCD in the curing agent component of the roll coating material for a paper machine is not particularly limited, but the roll coating material for a paper machine is a urethane elastomer whose deterioration is suppressed during paper making. From the viewpoint of composition, the range from 100:20 to 100:350 is preferable, the range from 100:20 to 100:250 is more preferable, and the range from 100:20 to 100:211 is even more preferable.

The mass ratio of the urethane prepolymer component of the roll coating material for a paper machine to the aliphatic PCD is not particularly limited, but the viewpoint that the roll coating material for a paper machine is composed of a urethane elastomer whose deterioration is suppressed during paper making. Therefore, the range from 100: 3 to 100:23 is preferable, the range from 100: 3 to 100:21 is more preferable, and the range from 100: 6.11 to 100: 19.3 is even more preferable.

Types and contents of urethane prepolymer component, curing agent component, aliphatic polyol and diisocyanate (TDI, etc.) in the urethane prepolymer component, and diamine-based curing agent and aliphatic PCD in the curing agent component of the roll coating material for a papermaking machine. The amount can be measured by a conventional measuring device (for example, a pyrolysis gas chromatograph (Py-GC), a Fourier transform infrared spectrophotometer (FT-IR), a nuclear magnetic resonance apparatus (NMR), etc.).

(Durometer A hardness on the surface)
The roll coating material for a paper machine is used in a range in which the durometer A hardness on the surface of the roll coating material for a paper machine is 65 or more and 99 or less, depending on the type of paper to be manufactured and the place of use in the paper machine. Will be done. More specifically, the durometer A hardness on the surface of the roll coating for paper machines is 70 or more and 99 or less, especially when used in a coating part (size part) where moisture resistance and chemical resistance are required. It is preferably 80 or more and 95 or less. Here, the durometer A hardness on the surface of the roll coating material for a paper machine is the hardness measured by the type A durometer.

[Embodiment 2: Roll for Paper Machine]
With reference to FIG. 1, the paper machine roll 10 of the present embodiment includes a roll core material 11 and a paper machine roll coating material 12 of the first embodiment that covers the outer periphery of the roll core material 11. Since the paper machine roll 10 of the present embodiment contains the paper machine roll covering material 12 of the first embodiment, deterioration of the urethane elastomer constituting the paper machine roll coating material is suppressed during paper making, so that paper making is performed. Does not adversely affect.

(Roll core material)
The roll core material 11 included in the paper machine roll 10 of the present embodiment is not particularly limited as long as it has mechanical strength that can be used as a paper machine roll, and is made of a metal such as iron or an iron alloy. .. An underlayer containing resin or FRP (fiber reinforced plastic) may be formed on the outer peripheral surface of the roll core material.

(Roll coating material for paper machines)
In the paper machine roll 10 of the present embodiment, the paper machine roll covering material 12 that covers the outer circumference of the roll core material 11 is the paper machine roll covering material of the first embodiment, and the description thereof will not be repeated here. At least one adhesive layer may be interposed between the outer peripheral surface of the roll core material 11 or the outer peripheral surface of the base layer and the inner peripheral surface of the roll coating material 12 for a paper machine.

(Manufacturing method for rolls for paper machines)
The method for producing the roll 10 for a paper machine according to the present embodiment is not particularly limited, and a conventional production method is preferably used. For example, the roll core material 11 is placed in the center of the cylindrical mold as it is or after the adhesive layer is formed, and the raw material (that is, urethane prepolymer and curing agent) of the roll coating material 12 for a paper machine is placed. By injecting and curing the roll core material 11, the roll coating material 12 for a paper machine that covers the outer periphery of the roll core material 11 can be formed.

1. 1. Preparation of Roll Coating Material Sample for Papermaking Machine With reference to Tables 1 to 3, in Examples 1 to 8 and Comparative Example 4, the urethane prepolymers (reactants of PTMG and TDI) shown in Tables 1 to 3 are used. A prepolymer (hereinafter also referred to as PTMG / TDI prepolymer) and a diamine-based curing agent (MOCA) and an aliphatic polycarbonate diol (aliphatic PCD) as curing agents are stirred and injected into a mold to be heat-cured. A urethane polymer, which is a roll coating material sample for a papermaking machine, was produced. Further, in Comparative Examples 1 to 3, the same as in each example, for the papermaking machine, except that only the diamine-based curing agent (MOCA) was used as the curing agent and the aliphatic polycarbonate diol (aliphatic PCD) was not used. A urethane elastomer as a roll coating material sample was prepared. Here, before stirring, the liquid temperature of the urethane prepolymer was 70 ° C., and the liquid temperature of the curing agent was 120 ° C. The defoaming condition of the urethane prepolymer before stirring was 70 ° C. for 3 hours. The stirring time was 1 minute. The mold temperature was 100 ° C. As for the heat curing conditions, the urethane elastomer was removed from the mold after 2 hours at 100 ° C., and then heated at 120 ° C. for 12 hours.

^{In Tables 1 to 3, Hyprene TM} L-167 (manufactured by Mitsui Chemicals, Inc., NCO mass%: 6.40) and Hyprene ^TM L-100 (manufactured by Mitsui Chemicals, Inc., NCO mass) are used as PTMG / TDI urethane prepolymers. %: 4.35) or ADIPRENE LF800A (manufactured by LANXESS, NCO mass%: 2.95) was used. Further, as MOCA, Curemine ^TM MT (manufactured by Kumiai Chemical Industry Co., Ltd., molecular weight: 267.15) was used. As an aliphatic PCD, Duranol ^TM T5650E (manufactured by Asahi Kasei Co., Ltd., appearance: viscous liquid, number average molecular weight: 500, OH value: 222.9 mgKOH / g), Duranol ^TM T5650J (manufactured by Asahi Kasei Co., Ltd., appearance: viscous liquid) , Number average molecular weight: 800, OH value: 139.5 mgKOH / g), Duranol ^TM T5651 (manufactured by Asahi Kasei Co., Ltd., Appearance: Viscous liquid, Number average molecular weight: 1000, OH value: 113.0 mgKOH / g), Duranol ^TM T5652 (Made by Asahi Kasei Co., Ltd., Appearance: Viscous liquid, Number average molecular weight: 2000, OH value: 56.7 mgKOH / g), Duranol ^TM T4691 (Made by Asahi Kasei Co., Ltd., Appearance: White solid, Number average molecular weight: 1000, OH value: 114.2 mgKOH / g) or Duranol ^TM T4692 (manufactured by Asahi Kasei Co., Ltd., appearance: white solid, number average molecular weight: 2000, OH value: 55.0 mgKOH / g) was used.

2. Immersion test of roll coating material sample for paper machine The degree of deterioration of the roll coating material sample for paper machine in the paper making of Examples 1 to 8 and Comparative Examples 1 to 3 obtained as described above. It was evaluated by the following immersion test. Here, the roll coating material samples for paper machines of Comparative Examples 1 to 3 correspond to those generally used in the past.

(1) Preparation of immersion liquid Size pine K-931 (manufactured by Arakawa Chemical Industry Co., Ltd.), which is a sizing agent used for paper making, is diluted with distilled water, and 10% by mass of size pine K-931 aqueous solution is used as the immersion liquid. Was prepared.

(2) Immersion test The roll coating material sample for a paper machine cut into a rectangular parallelepiped having a length of 40 mm, a width of 25 mm, and a height of 2 mm is immersed in the immersion liquid at a liquid temperature of 70 ° C. for 28 days, and then has a durometer A hardness. By measuring the amount of change and the rate of change in volume, the degree of deterioration of the roll coating material sample for the paper machine was evaluated. Here, the immersion test was carried out in the manner of JIS K6258: 2016 "Vulcanized rubber and thermoplastic rubber-How to determine liquid resistance". The smaller the amount of change in durometer hardness and the rate of change in volume, the smaller the degree of deterioration.

Here, the physical characteristics of the roll coating material sample for a paper machine depend on the initial durometer A hardness (before the immersion test), and the higher the initial durometer A hardness, the smaller the degree of deterioration, and the initial durometer A The lower the hardness, the greater the degree of deterioration tends to be. Therefore, a comparison was made between Examples and Comparative Examples having the same or similar initial durometer A hardness. That is, the results of Examples 1 to 8 and Comparative Examples 1 to 3 described above are compared with Example 1 (initial durometer A hardness is 92) and Comparative Example 1 (initial durometer A hardness is 96). Example 2 (initial durometer A hardness is 90) is summarized in Table 1, and Example 2 to Example 7 (initial durometer A hardness is 89 to 91) and Comparative Example 2 (initial durometer A hardness is 89 to 91). In comparison with 90), Table 2 summarizes Example 8 (initial durometer A hardness is 82), Comparative Example 3 (initial durometer A hardness is 82), and Comparative Example 4 (initial durometer A hardness is 58). And are summarized in Table 3.

With reference to Table 1, in Example 1, the amount of change in the hardness of the durometer A is 2 smaller than that of Comparative Example 1 and Comparative Example 2, which correspond to the roll covering materials for paper machines that have been generally used in the past. The volume change rate was reduced by 0.45 points to 1.58 points. From this, it was evaluated that Example 1 was excellent in terms of deterioration resistance, assuming that Comparative Example 1 and Comparative Example 2 were acceptable. Further, referring to Table 2, the hardness change amount of the durometer A hardness in Example 2 is smaller than that in Comparative Example 2, which corresponds to the roll coating material for a paper machine that has been generally used in the past. The volume change rate was 1.56 points smaller, and in Examples 3 to 7, the hardness change amount of the durometer A hardness was 1 smaller, and the volume change rate was 1.16 points to 1.32 points smaller. From this, it was evaluated that Example 2 was excellent and Examples 3 to 7 were good when Comparative Example 2 was allowed in terms of deterioration resistance. Further, referring to Table 3, in Example 8, the amount of change in the hardness of the durometer A is 2 smaller than that in Comparative Example 3, which corresponds to the roll coating material for a paper machine that has been generally used in the past. The volume change rate decreased by 2.24 points. Further, as compared with Comparative Example 4, in Example 8, the hardness change amount of the durometer A hardness was 3 smaller, and the volume change rate was 0.44 points smaller. From this, it was evaluated that Example 8 was excellent in terms of deterioration resistance, assuming that Comparative Example 3 was acceptable. In Comparative Example 4, the initial durometer A hardness was 58, which was evaluated as unsuitable because it was not suitable as a roll coating material for a paper machine.

It should be considered that the embodiments and examples disclosed this time are exemplary in all respects and are not restrictive. The scope of the present invention is shown by the claims rather than the above description, and it is intended to include all modifications within the meaning and scope equivalent to the claims.

10 rolls for paper machines, 11 roll core materials, 12 roll covering materials for paper machines.

Claims

Urethane prepolymer component, which is a reaction product of aliphatic polyol and diisocyanate,
Contains hardener components, including diamine-based hardeners and aliphatic polycarbonate diols,
A roll coating material for a paper machine having a durometer A hardness of 65 or more and 99 or less on the surface.
The roll coating material for a paper machine according to claim 1, wherein the content of the aliphatic polycarbonate diol is 2.5% by mass or more and 17.5% by mass or less.
The roll coating material for a paper machine according to claim 1 or 2, wherein the number average molecular weight of the aliphatic polycarbonate diol is 500 or more and 2000 or less.
The roll coating material for a paper machine according to any one of claims 1 to 3, wherein the mass ratio of the diamine-based curing agent to the aliphatic polycarbonate diol is in the range of 100:20 to 100:350.
The roll coating material for a paper machine according to any one of claims 1 to 4, wherein the mass ratio of the urethane prepolymer component to the aliphatic polycarbonate diol is in the range of 100: 3 to 100:23.
A roll for a paper machine, comprising a roll core material and a roll coating material for a paper machine according to any one of claims 1 to 5, which covers the outer periphery of the roll core material.